JP2013001825A - Ethylene-vinyl acetate copolymer composition and hardened product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ethylene-vinyl acetate copolymer composition which becomes an adhesive with excellent adhesiveness.SOLUTION: The ethylene-vinyl acetate copolymer composition contains an ethylene-vinyl acetate copolymer including 15-70 wt.% of a vinyl acetate residue unit and having an MFR of 50-10,000 g/10 min, and an organic solvent.

Description

  The present invention relates to an ethylene-vinyl acetate copolymer composition that becomes a cured product excellent in adhesiveness.

  Two-component adhesives are widely used because various materials can be easily bonded. In general, a two-component adhesive is composed of two types of a main component including a polyol component and a curing agent such as an isocyanate compound. The main component is mainly composed of a polyol such as a polyester polyol or a polyether polyol and an organic solvent as a main component. The performance of the adhesive greatly depends on the main component.

  A two-component adhesive using a polyether-based polyol such as polypropylene glycol as the main component has a problem that it is thermally deteriorated at a high temperature exceeding 120 ° C., although it is excellent in moisture and heat resistance. In addition, two-component adhesives using polyester-based polyols such as polyester as the main component have a disadvantage that they are deteriorated when left under high temperature and high humidity because they are excellent in heat resistance but poor in heat and humidity resistance. is doing. In order to solve these problems, a two-component adhesive (for example, see Patent Document 1) using hydrogenated polybutadiene polyol or the like has been proposed.

Japanese Patent Laying-Open No. 2002-26346 (refer to the claims)

  However, the two-component adhesive proposed in Patent Document 1 has a problem in adhesion because it has a certain effect in improving durability but is poorly mixed with an isocyanate compound.

  As a result of intensive studies to solve the above problems, the present inventors have excellent adhesiveness when a specific ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate copolymer composition comprising an organic solvent are used. The present inventors have found that a cured product can be obtained and have completed the present invention.

That is, the present invention relates to an ethylene-vinyl acetate copolymer that satisfies the following (A) to (B) and an ethylene-vinyl acetate copolymer composition containing an organic solvent, and a cured product using the same. Is.
(A) 15 to 70% by weight of vinyl acetate residue units measured according to JIS K6924-1 (1997 edition)
(B) Melt mass flow rate (hereinafter referred to as MFR) measured according to JIS K6924-1 (1997 version) is 50 to 10,000 g / 10 min. The present invention will be described in detail below.

The ethylene-vinyl acetate copolymer composition of the present invention is not particularly limited as long as it contains an ethylene-vinyl acetate copolymer that satisfies the following (A) to (B) and an organic solvent.
(A) 15 to 70% by weight of vinyl acetate residue units measured according to JIS K6924-1 (1997 edition)
(B) MFR measured according to JIS K6924-1 (1997 edition) is 50 to 10,000 g / 10 min. The vinyl acetate residue unit in the ethylene-vinyl acetate copolymer used in the present invention is 15 to 70% by weight. In particular, a saponified ethylene-vinyl acetate copolymer having a vinyl acetate residue unit of 20 to 50% by weight, more preferably 20 to 45% by weight, is preferable because of excellent adhesion. If it is less than 15% by weight, it may not be dissolved in an organic solvent at room temperature, and if it exceeds 70% by weight, the adhesiveness may be lowered.

  Further, the ethylene-vinyl acetate copolymer used in the present invention has an MFR of 50 to 10,000 g / 10 minutes, preferably 60 to 5000 g / 10 minutes, and more preferably 60 to 2400 g / 10 minutes. When the MFR is less than 50 g / 10 min, the viscosity is high and processability may deteriorate, and the ethylene-vinyl acetate copolymer composition may not flow at room temperature. If it exceeds 10,000 g / 10 minutes, the adhesive strength is inferior.

  Moreover, since the ethylene-vinyl acetate copolymer used in the present invention is an adhesive having particularly excellent adhesive strength, it preferably contains 0.01 to 10 mol% of vinyl alcohol residue units, More preferably, it contains 5.0 mol%.

  The ethylene-vinyl acetate copolymer is produced, for example, by a high pressure polymerization method, an emulsion polymerization method, or a solution polymerization method. The vinyl alcohol residue unit preferably contained can be obtained, for example, by hydrolyzing a vinyl acetate residue unit in an ethylene-vinyl acetate copolymer and saponifying it to a vinyl alcohol residue unit. In this case, for example, as a method of hydrolyzing an ethylene-vinyl acetate copolymer produced by a high pressure method, a method of performing a hydrolysis reaction using an alkali or acid such as sodium hydroxide as a catalyst, Specifically, a homogeneous saponification method in which an ethylene-vinyl acetate copolymer is dissolved in a good solvent and the reaction is carried out in a homogeneous system. Examples include a heterogeneous saponification method for carrying out the reaction.

  There is no restriction | limiting in particular in the organic solvent used for the ethylene-vinyl acetate type-copolymer composition of this invention, The organic solvent whose boiling point is 30 to 200 degreeC is preferable, and 40 to 150 degreeC is still more preferable.

  Examples of the organic solvent used in the present invention include aromatic organic solvents such as toluene and xylene, ester organic solvents such as ethyl acetate and butyl acetate, ketone organic solvents such as methyl ethyl ketone, chlorine organic solvents such as methylene chloride, Examples include ether organic solvents such as tetrahydrofuran, and these may be used alone or in combination of two or more. And since an adhesive excellent in workability is obtained, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, and methylene chloride are preferable, and toluene, xylene, ethyl acetate, butyl acetate, and methyl ethyl ketone are particularly preferable.

  The ethylene-vinyl acetate copolymer composition of the present invention preferably contains 1 to 80 parts by weight and 99 to 20 parts by weight of an ethylene-vinyl acetate copolymer and an organic solvent, respectively, and further 5 to 75 parts each. It is preferable to contain 95 to 25 parts by weight, and most preferably 15 to 50 parts by weight and 85 to 50 parts by weight, respectively. However, the total of the ethylene-vinyl acetate copolymer and the organic solvent is 100 parts by weight. When it is this content ratio, it is excellent in adhesive performance and workability.

  The ethylene-vinyl acetate copolymer composition of the present invention preferably further contains a reaction catalyst in order to enhance quick drying properties. Here, the reaction catalyst has an action of improving quick drying properties. The reaction catalyst is not particularly limited and known ones can be used. For example, amine catalysts such as triethylamine, triethylenediamine, N-methylmorpholine, tetramethyltin, tetraoctyltin, dimethyldioctyltin, triethyltin chloride Products, tin-based catalysts such as dibutyltin diacetate and dibutyltin dilaurate, phosphorus-based catalysts such as tributylphosphine and triphenylphosphine, monocarboxylic acids having 10 or more carbon atoms such as calcium stearate and sodium stearate, and Examples thereof include group 1 or group 2 metal salt catalysts selected from the periodic table of dicarboxylic acids, and one or more of these can be used. Among them, dibutyltin dilaurate is preferably used because of its high catalytic activity.

  The content of the reaction catalyst preferably contained is 0.0001 based on 100 parts by weight of the total of the ethylene-vinyl acetate copolymer and the organic solvent because the quick drying property of the obtained adhesive is improved. It is preferable to add ˜3 parts by weight, more preferably 0.0005 to 1 part by weight, and particularly preferably 0.001 to 0.5 part by weight.

  Moreover, since the ethylene-vinyl acetate type copolymer composition of this invention is excellent in durability, it is preferable to contain a carbodiimide compound. The carbodiimide compound may be any compound having one or more carbodiimide groups in the molecule. For example, N, N′-diisopropylcarbodiimide, N, N′-di (o-toluyl) carbodiimide, N, Monofunctional carbodiimide compounds such as N′-dicyclohexylcarbodiimide, N, N′-bis (2,6-diisopropylphenyl) carbodiimide; p-phenylene-bis (2,6-xylylcarbodiimide), p-phenylene-bis ( Bifunctional carbodiimide compounds such as t-butylcarbodiimide), p-phenylene-bis (mesitylcarbodiimide), tetramethylene-bis (t-butylcarbodiimide), cyclohexane-1,4-bis (methylene-t-butylcarbodiimide) ; Multifunctional carbodiimidization Goods and the like, polyfunctional carbodiimide compound among them is preferable. Examples of the monofunctional carbodiimide compound include (trade name) Stavaxol I (manufactured by Rhein Chemie), and examples of the polyfunctional carbodiimide compound include (trade name) Elasto Stub H01 (manufactured by Nisshinbo Co., Ltd.), Examples thereof include carbodiimide compounds generally known under trade names such as P (manufactured by Rhein Chemie), (trade name) Starvacol P-400 (manufactured by Rhein Chemie). One or more of these carbodiimide compounds can be used. The content of the carbodiimide compound that is preferably contained is 0.001 with respect to a total of 100 parts by weight of the ethylene-vinyl acetate copolymer and the organic solvent because the durability of the resulting adhesive is improved. It is preferable to add -5.0 weight part, 0.005-3.0 weight part is further more preferable, 0.01-2.0 weight part is especially preferable.

  There are no particular limitations on the production of the ethylene-vinyl acetate copolymer composition of the present invention, and any known method can be used. For example, a method of mixing an ethylene-vinyl acetate copolymer and an organic solvent at room temperature. The method of heating and mixing is mentioned, and the method of heating and mixing is preferably used because dissolution is fast. The temperature at the time of heating and mixing is preferably 30 to 150 ° C, particularly preferably 50 to 110 ° C.

  The ethylene-vinyl acetate copolymer composition of the present invention can be cured by reacting a curing agent. There is no restriction | limiting in particular in a hardening | curing agent, What kind of thing can be used if it can harden the ethylene-vinyl acetate type-copolymer composition of this invention.

  The curing agent used in the present invention is preferably bifunctional or higher because an adhesive having excellent adhesive strength can be obtained.

  As a hardening | curing agent, an isocyanate compound, an epoxy compound, etc. are mentioned, for example, An isocyanate compound and / or an epoxy compound are used preferably.

  Examples of the isocyanate compound include aromatic isocyanate compounds, aliphatic isocyanate compounds, alicyclic isocyanate compounds, and polyisocyanate derivatives thereof.

  Examples of the aromatic isocyanate compound include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4,4. '-Diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'-, or 2,2'-diphenylmethane diisocyanate or mixtures thereof) (MDI), 4,4'-toluidine diisocyanate (TODI) 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixtures thereof) (XDI), tetramethyl xylylene diisocyanate (1,3- or 1, -Tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), ω, ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene diisocyanate or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, etc. .

Examples of the aliphatic isocyanate compound include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene. Diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcapate, lysine diisocyanate, lysine ester triisocyanate, 1,6 , 11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate Door, decamethylene diisocyanate, and the like.
Examples of the alicyclic diisocyanate include monocyclic alicyclic diisocyanates and crosslinked cyclic alicyclic diisocyanates.

  Examples of the monocyclic alicyclic diisocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), and 3-isocyanate methyl-3. , 5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylene bis (cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylene bis (cyclohexyl isocyanate) or mixtures thereof) (water Added MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), bis (a Cyanatemethyl) cyclohexane (1,3- or 1,4-bis (isocyanatemethyl) cyclohexane or mixtures thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated) TDI), hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI), and the like.

Examples of the bridged cyclic alicyclic diisocyanate include norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, diisocyanatomethylbicycloheptane, di (isocyanatomethyl) tricyclodecane, and the like.
These polyisocyanate derivatives include, for example, multimers of the above isocyanate compounds (dimers, trimers, pentamers, heptamers, uretidinediones, uretonimines, isocyanurate modified products, polycarbodiimides, etc.), urethane modified products, etc. Body (for example, urethane-modified body in which a part of isocyanate group in the above-mentioned isocyanate compound or multimer is modified or reacted with monool or polyol), biuret-modified body (for example, biuret produced by reaction of the above isocyanate compound and water) Modified products, etc.), allophanate modified products (for example, allophanate modified products produced from the reaction of the above-mentioned isocyanate compound with a monol or polyol component), urea modified products (for example, produced by the reaction of the above isocyanate compound with a diamine). Ure Modified products, etc.), oxadiazinetrione (e.g., oxadiazinetrione produced by reaction of the isocyanate compound and a carbonic acid gas, etc.) and the like.
Among these derivatives, a derivative capable of forming a trifunctional or higher functional isocyanate group, for example, an adduct of the component having three or more active hydrogen atoms and the above isocyanate compound is preferable. Examples of the component having 3 or more active hydrogen atoms include tri- or more functional polyols such as C3-12 aliphatic polyols such as glycerin, trimethylolethane, trimethylolpropane, and sorbitol. Such an adduct is preferably an adduct having a low content of unreacted monomer. An adduct having a low unreacted monomer content can be produced by using a conventional separation and purification method such as thin-film distillation or extraction. The isocyanate content of the adduct is, for example, about 1 to 30% by weight, preferably about 3 to 25% by weight, and more preferably about 5 to 20% by weight.

  Said isocyanate compound may be used independently and may be used by 2 or more types.

  Specific products include “Coronate L”, “Coronate HL”, “Coronate 2030”, “Coronate 2031”, “Millionate MR”, “Millionate MTL” (trade name, manufactured by Nippon Polyurethane Co., Ltd.), “Takenate D- 102 ”,“ Takenate D-110N ”,“ Takenate D-200 ”,“ Takenate D-202 ”,“ Takenate 300S ”,“ Takenate 500 ”(trade name, manufactured by Takeda Pharmaceutical Co., Ltd.),“ Sumijour N3300 ”, “Sumijoule T-80”, “Sumijoule 44S”, “Sumijoule PF”, “Sumijoule L”, “Sumijoule N”, “Death Module L”, “Death Module IL”, “Death Module N”, “Death Module HL”, “Death Module T65”, “Death Module 15”, “Death Module” Le R "," Death module RF "," Death module SL "," Desmodur Z4273 "(trade name, manufactured by Sumika Bayer Urethane Co., Ltd.), and the like.

  Among them, an aromatic isocyanate compound is preferable because an adhesive having excellent adhesion durability is obtained. Diphenylmethane-4,4′-diisocyanate, tolylene diisocyanate, and adducts of these isocyanate compounds are particularly preferable, and diphenylmethane- Adducts of 4,4′-diisocyanate and / or tolylene diisocyanate and trimethylolpropane are preferred.

  The isocyanate compound is preferably a trifunctional or higher functional isocyanate compound because an adhesive having excellent adhesive strength can be obtained.

  Examples of the epoxy compound include monofunctional epoxy compounds such as phenyl glycidyl ether, lauryl glycidyl ether, phenoxypolyethylene glycol glycidyl ether, and benzoic acid glycidyl ether; terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and diglycidyl phthalate. Examples thereof include epoxy compounds such as esters, p-phenylene diglycidyl ether, diethylene glycol diglycidyl ester, diethylene glycol diglycidyl ether, 2,2-bis (4-glycidyloxyphenyl) propane, and bisphenol A type epoxy resin. A functional or higher epoxy compound is preferable, and 2,2-bis (4-glycidyloxyphenyl) propane is particularly preferable.

  These can be used alone or in combination of two or more.

  Further, the curing agent can be used alone or as a solution. Examples thereof include a solution composed of a curing agent and an organic solvent, an aqueous solution composed of a curing agent and water, a suspension, and a liquid curing agent. Of these, a solution comprising a curing agent and an organic solvent is preferable because an adhesive having excellent processability can be obtained.

  Examples of the organic solvent used when a solution comprising a curing agent and an organic solvent is used as the curing agent include aromatic organic solvents such as toluene and xylene, ester organic solvents such as ethyl acetate and butyl acetate, and ketones such as methyl ethyl ketone. Organic organic solvents, chlorinated organic solvents such as methylene chloride, and ether-based organic solvents such as tetrahydrofuran. These may be used alone or in combination of two or more. And since an adhesive excellent in workability is obtained, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, and methylene chloride are preferable, and toluene, xylene, ethyl acetate, butyl acetate, and methyl ethyl ketone are particularly preferable.

  The concentration of the curing agent when using a solution composed of a curing agent and an organic solvent as the curing agent is preferably 1 to 90% by weight, more preferably 10 to 75% by weight because an adhesive having excellent processability is obtained. .

  There is no particular limitation on the mixing method when using a solution comprising a curing agent and an organic solvent as a curing agent, and any known method can be used. For example, a method of mixing an isocyanate compound and an organic solvent at room temperature, a method of heating and mixing, etc. The method of mixing at room temperature is preferably used.

  The cured product of the present invention is obtained by mixing and reacting the ethylene-vinyl acetate copolymer composition of the present invention and the curing agent, and the blending ratio is not particularly limited as long as it becomes a cured product. Since a cured product having excellent adhesiveness can be obtained, the curing agent is preferably 0.01 to 150 parts by weight with respect to 100 parts by weight in total of the ethylene-vinyl acetate copolymer and the organic solvent. More preferably, it is -100 weight part, It is especially preferable that it is 0.1-50 weight part.

  And there is no restriction | limiting in particular in the method of mixing and mixing these, A well-known method can be used, For example, the method of mixing an ethylene-vinyl acetate type copolymer composition and a hardening | curing agent at room temperature, the method of heat-mixing etc. are mentioned. A method of mixing at room temperature is preferably used.

  Furthermore, the tylene-vinyl acetate copolymer composition of the present invention preferably contains an antioxidant because it can suppress coloration, and the antioxidant is not limited at all, for example, a phenolic antioxidant, Examples thereof include phosphorus antioxidants, sulfur antioxidants, amine antioxidants, lactone antioxidants, vitamin E antioxidants, and the like. These antioxidants can be used in combination of two or more in order to exhibit a greater effect. Moreover, as a compounding quantity of the antioxidant preferably added, since coloring can be suppressed, 0.001 to 1.0 part by weight with respect to a total of 100 parts by weight of the ethylene-vinyl acetate copolymer and the organic solvent. It is preferable to add, 0.001-0.5 weight part is further more preferable, and 0.001-0.1 weight part is especially preferable.

  Among these antioxidants, since the effect of suppressing coloring is large, 2,6-di-t-butyl-4-methylphenol and pentaerythritol tetrakis (3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate).

  The ethylene-vinyl acetate copolymer composition of the present invention may contain various additives as long as the effects of the present invention are not impaired. Examples of the various additives include dyes, organic pigments, inorganic pigments, inorganic reinforcing agents, plasticizers, processing aids such as acrylic processing aids, ultraviolet absorbers, light stabilizers, lubricants, waxes, crystal nucleating agents, plasticizers. Agent, mold release agent, hydrolysis inhibitor, antiblocking agent, antistatic agent, antifogging agent, antifungal agent, rust preventive agent, ion trap agent, flame retardant, flame retardant aid, inorganic filler, organic filler Etc.

  The ethylene-vinyl acetate copolymer composition of the present invention is, for example, a resin film, foam, cloth, nonwoven fabric, synthetic fiber, synthetic leather, leather, metal, metal oxide, rubber, thermoplastic elastomer, thermoplastic resin, It is useful for bonding thermosetting resins, paper, wood, glass, stone, ceramics, porcelain, and is particularly useful for adhesion such as laminate adhesion of resin films, sheets, molded products, and foams.

  The ethylene-vinyl acetate copolymer composition of the present invention includes, for example, leisure sheets, tents, greenhouses, veranda sheets, rain feathers, umbrellas, hoods, waterproof cloths, automobile cover sheets, architectural cover sheets, and solar cells. It is suitably used for bonding outdoor laminates used in outdoor environments such as backsheets. Moreover, it can be suitably used for bonding laminates for packaging in various industrial fields such as foods such as barrier films and retorts, beverages, pharmaceuticals and quasi drugs.

  The ethylene-vinyl acetate copolymer composition of the present invention is excellent in adhesiveness and useful in various fields.

  The present invention will be described in more detail based on the following examples. However, these are examples to help understanding of the present invention, and the present invention is not limited to these examples. Commercially available products were used unless otherwise specified.

(Reagents, etc.)
Reagents and the like used in Examples and Comparative Examples are represented using the following abbreviations.

<Ethylene-vinyl acetate copolymer>
EVA-1; Ultrasen (registered trademark) 727 (vinyl acetate residue unit content 28% by weight, MFR = 2200 g / 10 min), manufactured by Tosoh Corporation.
EVA-2; Ultrasen (registered trademark) 760 (vinyl acetate residue unit content 42 wt%, MFR = 70 g / 10 min), manufactured by Tosoh Corporation.
EVA-3; Ultrasen (registered trademark) 726-2 (vinyl acetate residue unit content 33% by weight, MFR = 700 g / 10 min), manufactured by Tosoh Corporation.
EVA-4; Ultrasen (registered trademark) 750 (vinyl acetate residue unit content 32% by weight, MFR = 30 g / 10 min), manufactured by Tosoh Corporation.
EVA-5; Ultrasen (registered trademark) 8A56A (vinyl acetate residue unit content 20% by weight, MFR = 30000 g / 10 min), manufactured by Tosoh Corporation.
EVA-6; LEVAPREN (registered trademark) 800HV (vinyl acetate residue unit content 80% by weight) manufactured by LANXESS.
EVA-7; Ultrasen (registered trademark) 685 (vinyl acetate residue unit content 14% by weight, MFR = 2500 g / 10 min), manufactured by Tosoh Corporation.

<Curing agent>
1) Isocyanate compound Isocyanate compound (A1); (trade name) Coronate L (ethyl acetate solution of adduct composed of tolylene diisocyanate and trimethylolpropane, isocyanate content 13.4% by weight), manufactured by Nippon Polyurethane Industry Co., Ltd.
Isocyanate compound (A2); (trade name) Coronate HX (isocinurate modified of hexamethylene diisocyanate, isocyanate content 21.0 wt%), manufactured by Nippon Polyurethane Industry Co., Ltd.
2) Epoxy compound Epoxy compound (E1); (trade name) Epicoat 828 (2,2-bis (4-glycidyloxyphenyl) propane), manufactured by Japan Epoxy Resins Co., Ltd. <carbodiimide compound>
Carbodiimide (C1); Elasto Stub (registered trademark) H01, manufactured by Nisshinbo Co., Ltd.

<Base material>
PET-1: Polyethylene terephthalate film, Melinex (registered trademark) type S (thickness: 100 μm), manufactured by Teijin DuPont Films Ltd.

(Physical property test method)
<Adhesive strength>
A test piece was cut out to a width of 25 mm, and the T-type peel strength was measured using a tensile tester ((trade name) Tensilon RTE-1210, manufactured by Orientec Corp.) to obtain an adhesive strength.

Example 1
In a 0.5 liter separable flask, 80 parts by weight of toluene, 5 parts by weight of ethyl acetate, and 15 parts by weight of EVA-1 were added, heated to 70 ° C. with stirring and dissolved for 1 hour, and then cooled. As a result, an ethylene-vinyl acetate copolymer composition was obtained. The obtained ethylene-vinyl acetate copolymer composition was fluid and showed fluidity.

  5 parts by weight of the isocyanate compound (A1) was added to and mixed with 100 parts by weight of the obtained ethylene-vinyl acetate copolymer composition to prepare an adhesive.

  The obtained adhesive was applied to the base material PET-1 using a spin coater ((trade name) 1H-DX, manufactured by Mikasa Co., Ltd.), and a dryer ((trade name) SPH-101, ESPEC Corporation). After drying at 100 ° C. for 1 minute in the company), PET-1 as another substrate and a bonded test piece were obtained.

  The obtained test piece was aged at 100 ° C. for 24 hours, and then the adhesive strength was measured. The results are shown in Table 1. It was found that the cured product obtained by reacting the obtained ethylene-vinyl acetate copolymer composition with a curing agent was excellent in adhesiveness.

Example 2
In a 0.5 liter separable flask, 50 parts by weight of xylene and 50 parts by weight of EVA-2 were placed, heated to 70 ° C. with stirring and dissolved over 1 hour, cooled, and then ethylene-vinyl acetate. A system copolymer composition was obtained. The obtained ethylene-vinyl acetate copolymer composition was fluid and showed fluidity.

  5 parts by weight of the isocyanate compound (A1) was added to and mixed with 100 parts by weight of the obtained ethylene-vinyl acetate copolymer composition to prepare an adhesive.

  A test piece was prepared in the same manner as in Example 1 using the obtained adhesive, and the adhesive strength was measured. The results are shown in Table 1. It was found that the cured product obtained by reacting the obtained ethylene-vinyl acetate copolymer composition with a curing agent was excellent in adhesiveness.

Example 3
In a 3 liter separable flask equipped with a stirring blade, 1000 ml of methanol, 300 g of EVA-1 and 5 g of sodium hydroxide were placed, heated to 45 ° C., and subjected to saponification reaction for 5 hours. After the reaction, the content was filtered, washed with methanol, neutralized, washed with water, and vacuum dried to obtain a saponified ethylene-vinyl acetate copolymer (hereinafter referred to as EVAOH-1). EVAOH-1 had a vinyl acetate residue unit content of 24% by weight, a vinyl alcohol residue unit of 1.6 mol%, and an MFR = 2250 g / 10 min.

  In a 0.5 liter separable flask, 80 parts by weight of toluene, 5 parts by weight of ethyl acetate, and 15 parts by weight of the obtained EVAOH-1 were added, heated to 60 ° C. with stirring, and over 1 hour. After dissolution, the mixture was cooled to obtain an ethylene-vinyl acetate copolymer composition. The obtained ethylene-vinyl acetate copolymer composition was fluid and showed fluidity.

  5 parts by weight of the isocyanate compound (A1) was added to and mixed with 100 parts by weight of the obtained ethylene-vinyl acetate copolymer composition to prepare an adhesive.

  A test piece was prepared in the same manner as in Example 1 using the obtained adhesive, and the adhesive strength was measured. The results are shown in Table 1. It was found that the cured product obtained by reacting the obtained ethylene-vinyl acetate copolymer composition with a curing agent was excellent in adhesiveness.

Example 4
In a 3 liter separable flask equipped with a stirring blade, 1000 ml of methanol, 300 g of EVA-3 and 5 g of sodium hydroxide were placed, heated to 45 ° C., and subjected to a saponification reaction for 2 hours. After the reaction, the content was filtered, washed with methanol, neutralized, washed with water, and vacuum dried to obtain a saponified ethylene-vinyl acetate copolymer (hereinafter referred to as EVAOH-2). EVAOH-2 had a vinyl acetate residue unit content of 32.3% by weight, a vinyl alcohol residue unit of 0.1 mol%, and MFR = 680 g / 10 min.

  In a 0.5 liter separable flask, 80 parts by weight of toluene, 5 parts by weight of methyl ethyl ketone, and 15 parts by weight of the obtained EVAOH-2 were placed, and heated to 70 ° C. with stirring, and dissolved over 1 hour. After cooling, 0.005 parts by weight of dibutyltin dilaurate was added as a reaction catalyst to 100 parts by weight of the ethylene-vinyl acetate copolymer composition to obtain an ethylene-vinyl acetate copolymer composition. The obtained ethylene-vinyl acetate copolymer composition was fluid and showed fluidity.

  An adhesive was prepared by adding 0.5 parts by weight of the isocyanate compound (A1) to 100.005 parts by weight of the obtained ethylene-vinyl acetate copolymer composition and mixing them.

  A test piece was prepared in the same manner as in Example 1 using the obtained adhesive, and the adhesive strength was measured. The results are shown in Table 1. It was found that the cured product obtained by reacting the obtained ethylene-vinyl acetate copolymer composition with a curing agent was excellent in adhesiveness.

Example 5
In a 3 liter separable flask equipped with a stirring blade, 1000 ml of methanol, 300 g of EVA-2, and 20 g of sodium hydroxide were placed, heated to 45 ° C., and subjected to saponification reaction for 1 hour. After the reaction, the content was filtered, washed with methanol, neutralized, washed with water, and vacuum dried to obtain a saponified ethylene-vinyl acetate copolymer (hereinafter referred to as EVAOH-3). EVAOH-3 had a vinyl acetate residue unit content of 35.8% by weight, a vinyl alcohol residue unit of 2.8 mol%, and MFR = 68 g / 10 min.

  In a 0.5 liter separable flask, 80 parts by weight of toluene, 5 parts by weight of butyl acetate, and 15 parts by weight of the obtained EVAOH-3 were added, heated to 60 ° C. with stirring, and over 1 hour. After dissolution, the mixture was cooled and 0.2 parts by weight of carbodiimide (C1) was added as a carbodiimide compound to 100 parts by weight of the ethylene-vinyl acetate copolymer composition to obtain an ethylene-vinyl acetate copolymer composition. . The obtained ethylene-vinyl acetate copolymer composition was fluid and showed fluidity.

  An isocyanate was prepared by adding 2.0 parts by weight of the isocyanate compound (A2) to 100.2 parts by weight of the resulting ethylene-vinyl acetate copolymer composition.

  A test piece was prepared in the same manner as in Example 1 using the obtained adhesive, and the adhesive strength was measured. The results are shown in Table 1. It was found that the cured product obtained by reacting the obtained ethylene-vinyl acetate copolymer composition with a curing agent was excellent in adhesiveness.

Example 6
After adding 85 parts by weight of toluene and 15 parts by weight of EVAOH-1 obtained in Example 3 to a 0.5 liter separable flask, the mixture was heated to 70 ° C. with stirring and dissolved over 1 hour. Cooled to obtain an ethylene-vinyl acetate copolymer composition. The obtained ethylene-vinyl acetate copolymer composition was fluid and showed fluidity.

  To 100 parts by weight of the obtained ethylene-vinyl acetate copolymer composition, 5 parts by weight of the epoxy compound (E1) was added and mixed to prepare an adhesive.

  A test piece was prepared in the same manner as in Example 1 using the obtained adhesive, and the adhesive strength was measured. The results are shown in Table 1. It was found that the cured product obtained by reacting the obtained ethylene-vinyl acetate copolymer composition with a curing agent was excellent in adhesiveness.

Comparative Example 1
In a 0.5 liter separable flask, 85 parts by weight of toluene and 15 parts by weight of EVA-4 were added, heated to 100 ° C. with stirring, dissolved over 1 hour, cooled, and ethylene-vinyl acetate. A system copolymer composition was obtained. The obtained ethylene-vinyl acetate copolymer composition was gel and did not exhibit fluidity. This is probably because MFR was too low.

Comparative Example 2
In a 0.5-liter separable flask, 85 parts by weight of toluene and 15 parts by weight of EVA-5 were added, heated to 100 ° C. with stirring, dissolved over 1 hour, cooled, and then ethylene-vinyl acetate. A system copolymer composition was obtained. The obtained ethylene-vinyl acetate copolymer composition was fluid and showed fluidity.

  5 parts by weight of isocyanate compound (A2) was added to and mixed with 100 parts by weight of the resulting ethylene-vinyl acetate copolymer composition to prepare an adhesive.

  A test piece was prepared in the same manner as in Example 1 using the obtained adhesive, and the adhesive strength was measured. The results are shown in Table 1. The cured product obtained by reacting the obtained ethylene-vinyl acetate copolymer composition with a curing agent was not excellent in adhesiveness. It seems that MFR is too high.

Comparative Example 3
In a 0.5 liter separable flask, 85 parts by weight of toluene and 15 parts by weight of EVA-6 were added, heated to 100 ° C. with stirring, dissolved over 1 hour, cooled, and then ethylene-vinyl acetate. A system copolymer composition was obtained. The obtained ethylene-vinyl acetate copolymer composition was fluid and showed fluidity.

  0.5 parts by weight of isocyanate compound (A1) was added to and mixed with 100 parts by weight of the obtained ethylene-vinyl acetate copolymer composition to prepare an adhesive.

  A test piece was prepared in the same manner as in Example 1 using the obtained adhesive, and the adhesive strength was measured. The results are shown in Table 1. The cured product obtained by reacting the obtained ethylene-vinyl acetate copolymer composition with a curing agent was not excellent in adhesiveness. This seems to be because there are too many vinyl acetate residue units.

Comparative Example 4
In a 0.5 liter separable flask, 85 parts by weight of toluene and 15 parts by weight of EVA-7 were added, heated to 100 ° C. with stirring, dissolved over 1 hour, cooled, and then ethylene-vinyl acetate. A system copolymer composition was obtained. The obtained ethylene-vinyl acetate copolymer composition was gel and did not exhibit fluidity. This is probably because there were too few vinyl acetate residue units.

Comparative Example 5
5 parts by weight of the isocyanate compound (A2) was added to 100 parts by weight of the EVAOH-3 obtained in Example 5. However, the EVAOH-3 could not be uniformly mixed at room temperature because it was a solid.

  Therefore, in order to obtain a uniform mixture, 100 parts by weight of EVAOH-3 and 5 parts by weight of isocyanate compound (A2) are added to Laboplast Mill Mixer R-60 (manufactured by Toyo Seiki Co., Ltd.), and the mixture is heated and melted at 120 ° C. did. The contents were thickened and could not be used as an adhesive. That is, it was not possible to uniformly mix at room temperature unless an organic solvent was blended.

Comparative Example 6
5 parts by weight of isocyanate compound (A1) was added to 100 parts by weight of toluene and mixed to prepare an adhesive.

  A test piece was prepared using the obtained adhesive in the same manner as in Example 1. However, the test piece was easily peeled off, and the adhesive strength could not be measured. This is probably because the ethylene-vinyl acetate copolymer was not blended.

  The ethylene-vinyl acetate copolymer composition of the present invention has excellent adhesion durability, and is extremely useful particularly in the field of adhesives.

Claims (8)

An ethylene-vinyl acetate copolymer containing an ethylene-vinyl acetate copolymer and an organic solvent satisfying the following (A) to (B).
(A) 15 to 70% by weight of vinyl acetate residue units measured according to JIS K6924-1 (1997 edition)
(B) Melt mass flow rate (hereinafter referred to as MFR) measured according to JIS K6924-1 (1997 edition) is 50 to 10,000 g / 10 min. The ethylene-vinyl acetate copolymer according to claim 1, wherein the ethylene-vinyl acetate copolymer further satisfies the following (C).
(C) 0.01-10 mol% of vinyl alcohol residue units 1 to 80 parts by weight of an ethylene-vinyl acetate copolymer and 99 to 20 parts by weight of an organic solvent (provided that the total of the ethylene-vinyl acetate copolymer and the organic solvent is 100 parts by weight) 2. The ethylene-vinyl acetate copolymer composition according to 2. The ethylene-vinyl acetate copolymer composition according to any one of claims 1 to 3, wherein the ethylene-vinyl acetate copolymer composition further contains a reaction catalyst. The ethylene-vinyl acetate copolymer composition according to any one of claims 1 to 4, wherein the ethylene-vinyl acetate copolymer composition further contains a carbodiimide compound. The ethylene-vinyl acetate copolymer composition according to any one of claims 1 to 5, wherein the organic solvent is at least one selected from the group consisting of toluene, xylene, ethyl acetate, butyl acetate and methyl ethyl ketone. A cured product obtained by reacting the ethylene-vinyl acetate copolymer composition according to any one of claims 1 to 6 with a curing agent. The cured product according to claim 6, wherein the curing agent is an isocyanate compound and / or an epoxy compound.