Adhesive composition for urethane foam

[Detailed Description of the Invention]

[Industrial Application] The present invention relates to the adhesive composition used for adhesion of automotive interior material. It is related with the water emulsion type adhesive composition used when pasting together in detail the outer skin material which used urethane foam as the substrate to the forming object part represented by a molded header, forming door, etc. [Description of the Prior Art] As for forming object parts, such as a molded header and a forming door, a polystyrene system plastic, a paint metal plate, hardboard, a resin board, corrugated paper, hard or the half-rigid urethane foam composite material, the glass mat, etc. are usually used as a substrate. As outer skin material pasted together to the above-mentioned forming object part, the urethane foam which carried out the lamination of VCM/PVC, the crossing, etc., polyethylene foam, and polypropylene form outer skin material are used. The adhesives for forming urethane foam outer skin material into compound material do not have a safety-and-hygiene problem, an environmental pollution problem, etc. in a manufacture factory, It is required that the adhesion admissibility over various automotive interior materials is large, that an adhesion layer is excellent in heat resistance, moisture resistance, and endurance, and also that the original cushioning properties of urethane foam and wind affinity should not be spoiled by osmosis of adhesives. former and automotive interior material (a composite material is called hereafter) -- business -- solvent adhesive, such as a urethane system, the Cros Rob Wren system, and an acrylonitrile butadiene rubber system, is mainly used, and adhesives are composite-material-ized by drying by heating adhesion or normal temperature adhesion. [Problem(s) to be Solved by the Invention] However, a solvent disperses at the time of work, and solvent adhesive has the danger of the labor safety problem in a factory, or a fire, and it is developing also into the pollution problem by environmental pollution, and the request of desolventizer type adhesives development is increasing also from a viewpoint of saving resources. Since the conventional solvent adhesive usually needed to apply adhesives to both forming object part and urethane foam outer skin material, the adhesives needs which can be pasted up by one side application from a workability side were growing. As the problem from the adhesion physical properties of the conventional adhesives, When it pastes together under conditions with insufficient dryness (namely, solvent scattering), while adhesive strength, heat resistance, etc. are missing and often causing exfoliation, The result which adhesives and a solvent permeate a urethane foam layer, and adhesives harden inside a form cell, In the case of urethane foam and chlorination vinyl sheet outer skin material, VCM/PVC is polluted by osmosis of a solvent and there is a crater or a problem that carry out blistering Phenomenon and commodity value falls remarkably at the same time the original cushioning properties of urethane foam or Texture is spoiled. On the other hand, although pressure sensitivity type acrylics emulsion system adhesives are beginning to be developed by the needs of the latest desolventizer type adhesives, improvement of one step is required of adhesiveness, heat resistance, workability, etc. now, and it has not resulted in utilization. for example, this artificer already described in JP,56-80451,A, JP,62-43475,A, and also a JP,62-96576,A specification as desolventizer type adhesives -- When (,) Combination of acrylics Copolymer worker ° Marcin which made acrylic ester and a vinylic halide compound the main ingredients, and an alkali catalyst, And the adhesives which combined adhesion grant resin water Desperaterone with these, It bases on latex compounds containing adhesion grant resin, such as an acrylic ester copolymer emulsion, methyl meta-arillate butadiene copolymer latex, and a styrene butadiene copolymer, acrylics copolymerization one which made the main ingredients chloro Bren latex, acrylic ester, and a vinylic halide compound -- an emulsion, an alkali catalyst, and heat reactivity phenol resin -- furthermore The water emulsion type adhesives possessing the adhesive strength for polyolefin forms which blended chlorinated polyethylene, heat resistance, moisture resistance, cushioning properties, A feeling, etc. were developed. However, among the latest composite material, the composite material produced the problem from the appearance of the foaming object in which the form intensity by shift to formation of deep-drawing fabrication and composition change of urethane foam increased, the rise of heat-resistant desired value, etc. practically, and is obliged to improvement so that it may be seen by a molded header, forming door, etc. That is, it is although it is applicable to outer skin material with low intensity of urethane foam itself enough in the adhesive composition described in the JP,56-80451,A specification, There is a problem in the urethane foam which has intensity, and on the relation which pasting within a time [ holding a semiarid condition, i.e., adhesiveness, / limited ] developed as a premise, adhesion tolerance level is narrow and the process top problem at the time of adhesion has arisen. The adhesive composition described in JP,62-43475,A and a 62-96576 item specification on the other hand, Since adhesive grant with polyethylene foam and polypropylene form was developed as a key objective, adhesion nature with urethane foam was spoiled at the time of high temperature, and has produced the problem that the conformity to the urethane foam which has especially intensity is missing. The object of the present invention is the Occupational Safety and Health problem by using a water emulsion type adhesive composition, It is the adhesiveness to various urethane foam, without solving an environmental pollution problem etc. and moreover spoiling the original cushioning properties and wind affinity of urethane foam, Adhesion tolerance level, i.e., good workability, is held, and it is in providing the adhesive composition holding the adhesive strength at the time of the heat under the heat resistance which should be provided as a composite material, and the high temperature atmosphere especially in deep-drawing fabrication object adhesion. [Means for Solving the Problem] styrene butadiene copolymer latex by which internal plasticization was carried out by polymerizing using acrylic ester and a chain transfer agent as a result of repeating examination wholeheartedly, in order that this artificer may achieve this object -- or Latex, such as a methylmetaacrylate butadiene copolymer, was made into the main ingredients, and it finds out that it is very effective in adhesiveness with various urethane foam, and heat resistance to combine chloroprene latex, adhesion grant resin, and an alkaline catalyst, and came to complete the present invention. Namely, the present invention a) As opposed to one copy of solid content 100ffi of styrene butadiene copolymer latex or methylmetaacrylate butadiene copolymer latex which copolymerized acrylic ester under existence of a chain transfer agent, b) It is an adhesive composition for urethane foam which makes solid content 1~100 weight section C adhesion grant resin by making chloro Bren latex into solid content, and blends 0.01~10 weight sections by making a 1~100 weight section d weight section power Li catalyst into solid content. SBR used for the present invention or MBR latex makes styrene or a methylmetaacrylate, and butadiene the main ingredients, and names generically what copolymerized acrylic ester and a functionality monomer under existence of a chain transfer agent. As for a rate that 0~-40-degreeC and a gel content, i.e., latex polymer, do not dissolve polymer glass transition temperature of latex in toluene, what is less than 40 % of the weight is preferred. . As acrylic ester, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, lauryl methacrylate, etc. are mentioned. They are acrylic acid, meta-acrylic acid, itaconic acid, and crotonic acid as a functional group monomer, Maleic acid, acryl amide, meta-acryl amide, n-Methylol acryl amide, hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, etc. are mentioned. A carbon tetrachloride, n-Dodecyl mercaptan, t-Dodecyl mercaptan, etc. are mentioned as a chain transfer agent. As a copolymer desirable in these, they are stability at the time of an emulsification polymerization, and adhesion physical properties, Let styrene or a methylmetaacrylate, and butadiene be the main ingredients from an economical efficiency side, They are butyl acrylate or 2-ethylhexyl acrylate as acrylic ester, As a functional group monomer, what copolymerized under existence of n-Dodecyl mercaptan or t-Dodecyl mercaptan considering a kind of acrylic acid, itaconic acid, acryl amide, and hydroxyethyl acrylate or two sorts or more of combination as a chain transfer agent is preferred. About a ratio of styrene or a methylmetaacrylate, and butadiene, ranges of a copolymerization rate of these monomers are 20/80~80/20 in a weight ratio. Preferably it is 40/60~60/40. When butadiene exceeds 80% by a weight ratio, stability at the time of an emulsification polymerization, adhesive strength, heat resistance, etc. are spoiled, and when it is less than 20%, a problem is produced in adhesiveness. A range of a copolymerization rate of acrylic ester is 1~511 copies among 100 weight sections of all the monomers, and preferably a range of it is 5~20 weight sections. When more than 50 weight sections, adhesive strength and heat resistance are spoiled, when less than 1 weight section, the internal plastic effect is very low, adhesion nature with urethane foam is missing, and there are not satisfaction and To about the object of the present invention. The range of 1~20 weight sections, preferably a range of a copolymerization rate of a functional group monomer are 2~10 weight sections among 100 weight sections of all the monomers. When less than 1 weight section, stability at the time of an emulsification polymerization is spoiled, and stable copolymer latex is not obtained, and heat resistance is spoiled remarkably. While adhesion nature with urethane foam is missing in order that stability at the time of an emulsification polymerization may be spoiled, and stable copolymer latex may not be obtained and latex polymer may become hard when more than 20 weight sections, there is a problem also from an economical efficiency side. The range of 0.1~5.0 weight sections, preferably a range of a rate of a chain transfer agent are 1~3 weight sections to 100 copies of all the monomers. When less than 0.1 weight section, the internal plastic effect of latex is very low, adhesion nature with urethane foam is missing, and when more than 5 weight sections, a molecular weight of copolymer polymer falls remarkably and produces a problem in adhesive strength and heat resistance. About chloroprene latex used for the present invention, 40~70% of solid content by which the present upper tone is carried out preferably 50~60%, viscosity of 10~10000 c.p.s. preferably 10~500 c.p.s., Pi (un-denaturing of 7~13 or carboxyl group denaturation type chloroprene latex is mentioned.) Preferably a crystallization speed is quick and a type excellent in cohesive force is desirable. The object of the chloroprene latex use is in improvement in adhesive strength at the time of normal temperature using crystallinity which polymer has, and heat, and various kinds of adhesive improvement. A range of a combination rate of the chloroprene latex is 1~100 weight sections to 100 weight sections of solid content of SBR or MBR latex. Preferably it is the range of 5~50 weight sections. When less than 1 weight section, adhesion nature with urethane foam and heat-resistant improvement are not found, but when more than 100 weight sections, compatibility with SBR or MBR latex is missing, a dry tunic becomes cloudy, pressure-sensitivity and adhesion nature to urethane foam fall, and practicality is missing. As adhesion grant resin used for the present invention, it is glycerin ester of nature or polymerization rosin, denaturation Logic * A, and Hydrogenation rosin, Rosin system adhesion grant resin represented by triethylene glycol ester and Penta erythritol ester, alpha-pinene, beta-pinene, Dipentene, Terpene phenol, terpene series resin, fatty series system petroleum resin, Aromatic system petroleum resin, Alkyl phenol resin, coumarone-indene resin, xylene resin, etc. are mentioned. On a relation blended with inside of this etc., preferably SBR or MBR latex, As water Death version type adhesion grant resin with desirable water Death version type adhesion grant resin, it is 40~60% of solid content, Viscosity 100~l000c.p.s., Terpene phenol resin of PH5~11, Phenol resin, fatty series system petroleum resin, glycerin ester of rosin, Water Death version, such as triethylene glycol ester, diethylene glycol ester, and Penta erythritol ester, are mentioned, and it is a combination rate of the adhesion grant resin, It is the range of 1~100 weight sections, preferably 10~50 copies to 100 weight sections of solid content of SBR or MBR latex. When less than 1 weight section, adhesion nature with urethane foam and pressure-sensitivity are missing, when more than 100 weight sections, heat resistance is spoiled and practicality is missing. As the alkaline catalyst used for the present invention, Ethylene diamine, diethylene triamine, Triethylene tetramine, Inorganic system alkalinity catalysts, such as amine system alkalinity catalysts, such as hexamethylenetetramine, ammonium carbonate, potassium carbonate, potassium sodium carbonate, guanidine carbonate, carbonic acid zirconyl ammonium, ammonium acid carbonate, potassium bicarbonate, and sodium bicarbonate, are mentioned. Among this etc., an inorganic system alkalinity catalyst is indispensable and is preferred. [ of combined use of a kind of an inorganic system alkalinity catalyst, two sorts or more, or an inorganic system alkalinity catalyst and an amine system alkalinity catalyst ] An alkaline catalyst is good to use as solution. Combination rates of this alkaline catalyst are the range of the amount part of 0 *01~IQM(s), preferably 0.2~5 weight sections to 100 weight sections of solid content of SBR or MBR latex. Heat resistance is missing, when less than 0.01 weight section, when more than 10 weight sections, an adhesion performance target does not have trouble in particular, but when using as solution, a solid content fall of adhesives is caused and it is a problem practically. An adhesive composition for this urethane foam accepts necessity, and is polyvinyl alcohol, Thickeners, such as hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylic acid, polyacrylic acid soda, polyacrylic acid ammonium, and a Nonion system surface-active agent, are made into the start, An antiaging agent, an antifoaming agent, a leveling agent, colorant, a Cissing prevention agent, a vulcanizing agent, a rubber accelerator, etc. may be added and used. As mentioned above, since adhesive compositions for urethane foam of the present invention are water emulsion type adhesives in formation of compound material of automotive interior material, there are very few Occupational Safety and Health problems and environmental pollution problems. and One form -- without it spoils original cushioning properties and wind affinity -- adhesiveness to various urethane foam, Since it excels in adhesive strength at the time of heat under heat resistance which should hold adhesion admissibility, i.e., good workability, and should be provided as a composite material, and high temperature atmosphere especially in deep-drawing fabrication object adhesion, practical use value is very high. [Example] Next, although the example of manufacture, an example, and a comparative example explain concretely, the present invention is not limited to the following examples. As long as there is no specification especially in below, a part and % are based on a weight standard. Example 1~6 of manufacture Into the autoclave provided with the stirrer which carried out replacement by nitrogen gas in which temperature control is possible, 100 copies of distilled water, 1.0 copy of Dodecylbenzenesulfur water A acid soda, 0.5 copy of potassium persulfate, and 100 copies of monomers and the chain transfer agent that are shown in table-1 were taught, and the emulsification polymerization was carried out in 60~65 degreeC for 20 hours. The potassium hydrate adjusted copolymer latex after the end of a polymerization to PH7~8, steam stripping was performed, the remains monomer was removed, and SBR of 50% of the solid content used for the present invention or MBR latex was obtained. Example 1-16 SBR or 100 weight sections of MBR latex obtained in example 1~6 of manufacture is put into a container with a stirrer, Agitating, addition mixture was carried out at a rate shown in table-2 at the order of chloro Bren latex, adhesion grant resin, and an alkaline catalyst, and it set to 5000CPS in hydroxy cell loss solution 5%, and obtained the adhesive composition for urethane foam of the present invention. The composite material was created on the conditions shown below using the adhesive composition, as following, the physical-properties examination was presented and the result was shown in table-3. l) Adhesion conditions b) The frame lamination of the crossing was carried out as a resin board (plate which carried out hot forming of waste textile by phenol resin) mouth urethane foam outer skin of forming object board---three-copy thickness, Polyether type Ha Paint for the following brand facilities made from Bridgestonen tire ■ Cloth---Hitachi spray gun As-30-10 type is used, and it is uniform application Hot dry about the adhesives of 150 g / Vo (net) to a resin board. Resin board which carried out the Dry-adhesives application It is oven time (it is time of pasting after extraction from drier)---1 minute to dryness for 2 minutes in a 100 degreeC hot air dryer. However, adhesion admissibility is described separately. A) Contact It wears, various urethane foam is pasted together 1 minute after - open time, and they are 0 and 5 kg. ; It was stuck by pressure for 10 seconds by /cj closing pressure power, and the composite material for various physical-properties examinations was created. Chi) # The various physical-properties examinations after care of health were raw-room temperature presented on the 1st. However, about initial-bond-strength measurement, it measured 10 minutes afterward. 2) Physical-properties examination b) Adhesion admissibility Various urethane foam was pasted together 5 minutes after dryness as the check method of adhesion tolerance level, 1 minute after adhesion, the resin board and the urethane foam adhesion layer were compulsorily exfoliated in the fingertip, the adhesion state was displayed as following, and the result was shown in table-3. O To perfect mother's body destruction of - urethane foam -.. A part of mother's body destruction x ... Various urethane foam is pasted together 5 minutes after the initial adhesiveness dryness of an exfoliation mouth of the interfaces of , A composite material is judged in 125X25-mm size 5 minutes after adhesion, 50 big-building urethane foam is removed from an end, and it is considered as a sample, The sample was held in the direction of 180"C to the tensilon tension tester, peel strength was measured under 23±2degreeC and RH65% of homoiothermal homoiothermy conditions, and the display showed the result to table-3 as following. O ..- It pulls and is a urethane foam mother's body destructive rate per area. 100%O~, -50~99%delta, and -20~49% x ... According to the initial-bond-strength measuring method of the above-mentioned mouth, peel strength was measured for the composite material one day after 0~19% Ha normal-state adhesive strength care of health, and the same display showed the result to table-3. 2) Heat-resistant adhesive strength According to the measuring method of the above-mentioned mouth, peel strength was measured for the composite material one day after care of health under the atmosphere of 110 ±2-degreeC, the result was pulled, and it expressed to table-3 as the urethane foam mother's body destruction per area, and a rate (%). The combination materials of table-2 display are as following. b) 50% of Denka chloroprene latex (product made from DENKI KAGAKU KOGYO ■) LA-50 and - solid content L V -60--# 60% The 50% of solid content water Desper gitane of mouth Stacon 2130R (product made from Yasuhara oil and fat industry ■) Terpene phenol resin C) 50% of super ester E7io< solid content water Desper gitane of product denaturation rosin ester resin for roughness made from chemical industry ■ D) 50% of solid content water Death version of fin ton EQ9503 (product made from Nippon Zeon ■) aliphatic-hydrocarbon resin Ho) 20%K1IC0ff solution Solution of potassium bicarbonate What) 2%KIICOs/IIMT^solution potassium bicarbonate / hexamethylenetetramine = solution of 2/1 mixture Comparative example 1 As opposed to 1011 copies of solid content of styrene butadiene copolymer latex (the product made from three-piece east pressure chemicals KK, brand name poly rack 750, the solid content of 48%, the viscosity of 150 c.p.s., PH6, 5, 25% of glass-transition-temperature =10-degreeC1 gel content), They are 30 copies about Denka chloroprene latex LA-50 like Example 1, The adhesive composition which set Stacon 213OR as 20 copies and 20%KHCO, and set solution as the viscosity of 5000 c.p.s. in hydroxy cellulose solution two copies and also 5% was obtained, the composite material was created by the method which applied to the example correspondingly below, the physical-properties examination was presented, and the result was shown in table-3. Comparative example 2 The adhesive composition which only Denka chloroprene latex LA-50 excepted from example-1 was obtained, the composite material was created by the method which applied to the example correspondingly below, the physical-properties examination was presented, and the result was shown in table-3. Comparative example 3 The adhesive composition which only Stacon 2130 R excepted from example-1 was obtained, the composite material was created by the method which applied to the example correspondingly below, the physical-properties examination was presented, and the result was shown in table-3. Comparative example 4 The adhesive composition which only KHCO3 solution excepted example~1 to 20% was obtained, the composite material was created by the method which applied to the example correspondingly below, the physical-properties examination was presented, and the result was shown in table-3. Comparative example 5 The adhesive composition which was used in Example 1 and which set the SBR latex obtained in example I of manufacture as hydroxyethyl cellulose solution 5% at the viscosity of 5000 c.p.s. was obtained, the composite material was created by the method which applied to the example correspondingly below, the physical-properties examination was presented, and the result was shown in table-3. Table -One [Effect of the Invention] The adhesive composition for urethane foam of the present invention, In the formation of compound material of automotive interior material, SBR by which internal plasticization was carried out makes MBR latex the main ingredients, Although it is chloroprene latex, adhesion grant resin, and also the water emulsion type adhesives that have the pressure-sensitivity which blended the alkaline catalyst, Since it is adhesives with adhesiveness with the various urethane foam which should be provided as adhesives for automotive interior material, initial bond strength, adhesion admissibility, and also high heat resistance, practical use value is very high also from fields, such as Occupational Safety and Health and environmental pollution, and the meaning is size.