JP2019112594A - Resin composition for bonding, primer, adhesive agent and article - Google Patents

Abstract

To provide a resin composition for bonding capable of forming a coated film which is excellent in various physical properties such as storage stability, adhesion between a difficult-to-attach substrate and different base materials, and weather resistance.SOLUTION: There is provided a resin composition for bonding in which a composite resin (A) formed by bonding polysiloxane (a1) having a structural unit (U1) containing an aromatic hydrocarbon substituent and a structural unit (U2) containing no aromatic hydrocarbon substituent, and a polymer having a group reacting with (a1) by Formula (4) is dissolved or dispersed in a medium, the polysiloxane (a1) in the composite resin (A) is 75-99 mass%, and the structural unit (U1) in the polysiloxane (a1) is 10-55 mass%.SELECTED DRAWING: None

Description

  The present invention relates to an adhesive resin composition, a primer, an adhesive and an article.

  In recent years, development of high performance materials combining the properties of inorganic materials and organic materials has been widely carried out in each industrial field, and inorganic materials have excellent durability such as weather resistance, heat resistance and scratch resistance, and organic materials Is generally known to be rich in flexibility and processability. Among these, a curable resin composition in which an inorganic material and an organic material are complexed has been proposed (see, for example, Patent Document 1). Although this curable resin composition can obtain a coating film excellent in various physical properties such as weather resistance, heat resistance, etc., in order to be applied to a difficultly adhering substrate such as polypropylene or adhesion between different materials, the adhesiveness is It was not enough.

  Then, while it is excellent in various physical properties, such as a weather resistance, the material applicable to adhesion between a poor adhesion base material and a dissimilar material was called for.

Patent No. 3521431 gazette

  The problem to be solved by the present invention is an adhesive resin which is excellent in storage stability and can form a coating film excellent in various physical properties such as adhesion between a poor adhesion substrate and different materials, weatherability, heat resistance and the like. It is an object of the present invention to provide an article having a composition, a primer, an adhesive and a coating of the adhesive resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition for adhesion in which a specific resin and a composite resin to which a specific polymer segment is bonded is dissolved or dispersed in a medium is stored. The inventors have found that it is possible to form a coating film which is excellent in stability and excellent in various physical properties such as adhesion between a hardly adhering substrate and different materials, weatherability, heat resistance and the like, and the present invention has been completed.

  That is, in the present invention, a polysiloxane (a1) having a structural unit (U1) represented by the general formula (1) or (2) and a structural unit (U2) represented by the general formula (3) and a polymer An adhesive resin composition in which a composite resin (A) in which (a2) and (a) are bonded by a bond represented by the general formula (4) is dissolved or dispersed in a medium, and in the composite resin (A) The resin composition for adhesion is characterized in that the polysiloxane (a1) is 75 to 99% by mass, and the structural unit (U1) in the polysiloxane (a1) is 10 to 55% by mass.

（一般式（１）、（２）中のＲ^１は芳香族炭化水素置換基を表し、Ｒ^２は芳香族炭化水素置換基又はアルキル基を表す。）

(R ¹ in the general formulas (1) and (2) represents an aromatic hydrocarbon substituent, and R ² represents an aromatic hydrocarbon substituent or an alkyl group.)

（一般式（３）中のＲ^３はメチル基又はエチル基を表す。）

(R ³ in general formula (3) represents a methyl group or an ethyl group.)

  The resin composition for adhesion of the present invention can form a coating film excellent in various physical properties such as adhesion between a low adhesion substrate and different materials, weatherability, etc. It can be used.

  The adhesive resin composition of the present invention comprises a polysiloxane (a1) having a structural unit (U1) represented by the general formula (1) or (2) and a structural unit (U2) represented by the general formula (3) The resin composition for adhesion, wherein the composite resin (A) in which the polymer (a2) and the polymer (a2) are bonded by the bond represented by the general formula (4) is dissolved or dispersed in a medium, The polysiloxane (a1) in (A) is 75 to 99% by mass, and the structural unit (U1) in the polysiloxane (a1) is 10 to 55% by mass.

  First, the composite resin (A) will be described. The composite resin (A) is obtained by bonding the polysiloxane (a1) and the polymer (a2) by a bond represented by the general formula (4).

  As a form of the composite resin (A), for example, a composite resin having a graft structure in which the polysiloxane (a1) is chemically bonded as a side chain of the polymer (a2), or the polymer (a2) Composite resin etc. which have the block structure which the said polysiloxane (a1) couple | bonded chemically are mentioned.

  The bond represented by the general formula (4) is a silanol group and / or a hydrolyzable silyl group which the polysiloxane (a1) has, and a silanol group and / or a hydrolyzable silyl which the polymer (a2) has. It is generated by dehydration condensation reaction with a group. Accordingly, in the general formula (4), a carbon atom constitutes a part of the polymer (a2), and a silicon atom bonded only to an oxygen atom constitutes a part of the polysiloxane (a1).

  It is important that the amount of the polysiloxane (a1) in the composite resin (A) is 75 to 99% by mass, but a coating film having more excellent adhesion, heat resistance and weatherability can be obtained, so 80 It is preferable that it is -98 mass%, and it is more preferable that it is 85-95 mass%.

  The mass ratio of the polysiloxane (a1) is based on the preparation ratio of the raw materials used for the production of the composite resin (A), and the formation of by-products such as methanol and ethanol which can be generated by hydrolysis condensation reaction It is a value calculated taking into consideration.

  The polysiloxane (a1) has a chain structure composed of a silicon atom and an oxygen atom, and has a hydrolyzable silyl group and / or a silanol group.

  The hydrolyzable silyl group is an atomic group in which a hydrolyzable group is directly bonded to the silicon atom, and has, for example, a structure represented by the following general formula (5).

（式中、Ｒ^４はアルキル基、アリール基またはアラルキル基等の１価の有機基を、Ｒ^５はハロゲン原子、アルコキシ基、アシロキシ基、フェノキシ基、アリールオキシ基、メルカプト基、アミノ基、アミド基、アミノオキシ基、イミノオキシ基またはアルケニルオキシ基である。また、ｎは０〜２の整数である。）

(Wherein R ⁴ is a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group, and R ⁵ is a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, a mercapto group, an amino group, an amide Group, aminooxy group, iminooxy group or alkenyloxy group, and n is an integer of 0 to 2.)

  The hydrolyzable group is capable of forming a hydroxyl group under the influence of water, and includes, for example, a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, a mercapto group, an amino group, an amide group Groups, iminooxy groups, alkenyloxy groups and the like are mentioned, and among them, alkoxy groups and substituted alkoxy groups are preferable.

  The silanol group is an atomic group in which a hydroxyl group is directly bonded to the silicon atom, and is formed when the hydrolyzable silyl group is hydrolyzed.

  Since the said polysiloxane (a1) is excellent in storage stability and a coating film excellent in adhesiveness is obtained, 10-55 mass of structural units (U1) represented by the said General formula (1) or (2) It is important to have%, but it is more preferable to have 10 to 40% by mass.

  Moreover, since the said polysiloxane (a1) is a coating film which is excellent in a weather resistance and heat resistance, it is important that it has 10 mass% or more of structural units (U2) represented by the said General formula (3). It is preferable to have 15% by mass or more.

  The polysiloxane (a1) is a structural unit other than the structural unit (U1) and the structural unit (U2), for example, a structural unit (U3) represented by the following general formula (6) or (7), etc. It can have.

（一般式（６）、（７）中のＲ^６は芳香族炭化水素置換基以外の炭素原子数が３〜１２の有機基を表し、Ｒ^７及びＲ^８はそれぞれ独立してメチル基又はエチル基を表す。）

(R ⁶ in the general formulas (6) and (7) represents an organic group having 3 to 12 carbon atoms other than an aromatic hydrocarbon substituent, and R ⁷ and R ⁸ each independently represent a methyl group or an ethyl group Represents a group)

  As said polysiloxane (a1), what is obtained by carrying out the hydrolysis condensation of the silane compound mentioned later completely or partially can be used, for example.

  The structural unit (U1) of the polysiloxane (a1) has, for example, an aromatic ring such as phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, phenyltrichlorosilane, diphenyldichlorosilane, etc. By using a silane compound or a partial hydrolytic condensate thereof, etc., it can be easily introduced into the polysiloxane (a1), but among these, the storage stability and the adhesiveness are further improved. It is preferable to use phenyltrimethoxysilane or diphenyldimethoxysilane.

  The structural unit (U2) is, for example, a silane compound such as methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, methyltrichlorosilane, ethyltrichlorosilane, etc. And the partial hydrolysis condensates thereof can be easily introduced into the polysiloxane (a1).

  The structural unit (U3) is, for example, n-propyltrimethoxysilane, iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane, vinyltrimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (Meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltrichlorosilane, vinyltrichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, methylcyclohexyldimethoxysilane, It is easily introduced into the polysiloxane (a1) by using silane compounds such as dimethyldichlorosilane and diethyldichlorosilane, and partial hydrolytic condensates thereof. Rukoto can.

  These silane compounds may be used alone or in combination of two or more.

  The polymer (a2) has a hydrolyzable silyl group and / or a silanol group capable of reacting with the polysiloxane (a1).

  As the polymer (a2), it is preferable to use one having a number average molecular weight of 3,000 to 100,000, since the storage stability is excellent and the adhesion of the obtained coating film is further improved. It is more preferred to use those having a number average molecular weight of 5,000 to 25,000. Here, the number average molecular weight is a value converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC") measurement.

  Examples of the polymer (a2) include vinyl polymers such as acrylic polymers, fluoroolefin polymers, vinyl ester polymers, and aromatic vinyl polymers; polyester resins, alkyd resins, polyurethane resins, etc. Vinyl polymers are preferable because they are excellent in storage stability and the adhesion of the resulting coating film is further improved.

  As the vinyl polymer, for example, those produced by polymerizing various vinyl monomers in an organic solvent in the presence of a polymerization initiator can be used.

  The hydrolyzable silyl group can be easily introduced into the vinyl polymer, for example, by polymerizing a vinyl monomer having a hydrolyzable silyl group.

  Examples of the vinyl monomer having a hydrolyzable silyl group include vinyltrimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane or 3- (meth) Acryloyloxypropylmethyldimethoxysilane etc. can be used, and among them, it is preferable to use 3- (meth) acryloyloxypropyltrimethoxysilane.

  Examples of the raw material of the vinyl polymer other than the vinyl monomer having the hydrolyzable silyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) ) (Meth) acrylic acid ester compounds such as acrylate and cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate A vinyl monomer having a hydroxyl group such as acrylate), polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, glycerol mono (meth) acrylate; methoxypolyethylene Glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxy polyethylene glycol-polypropylene glycol (meth) acrylate phenoxy polyethylene glycol-polypropylene glycol (meth) acrylate Etc., a vinyl monomer having a polyoxyalkylene group in which the end is capped with an alkoxy group or a phenoxy group; a vinyl monomer having a tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate; -A vinyl monomer having a secondary amino group such as methylaminoethyl (meth) acrylate; a single monomer having a primary amino group such as aminomethyl acrylate Vinyl monomer having a group having a basic nitrogen atom such as; vinyl monomer having a fluorine atom such as 2,2,2-trifluoroethyl (meth) acrylate; vinyl ester compounds such as vinyl acetate; methyl vinyl ether Vinyl compounds such as (N); nitrile compounds of unsaturated carboxylic acids such as (meth) acrylonitrile; vinyl compounds having an aromatic ring such as styrene; α-olefin compounds such as isoprene; vinyl having an epoxy group such as glycidyl (meth) acrylate Monomers; vinyl monomers having an amide group such as (meth) acrylamide; methylolamide groups such as N-methylol (meth) acrylamide and vinyl monomers having an alkoxy compound thereof; 2-aziridinylethyl (meth) ) Vinyl monomers having an aziridinyl group such as acrylates; Ta) Vinyl monomer having isocyanate group such as acryloyl isocyanate and / or blocked isocyanate group; Vinyl monomer having oxazoline group such as 2-isopropenyl-2-oxazoline; Dicyclopentenyl (meth) Vinyl monomers having a cyclopentenyl group such as acrylates; vinyl monomers having a carbonyl group such as acrolein; vinyl monomers having an acetoacetyl group such as acetoacetoxyethyl (meth) acrylate; (meth) acrylic acid It is possible to use monomers having a carboxyl group such as itaconic acid, maleic acid or their half esters or their salts.

  Examples of the organic solvent that can be used when producing the vinyl polymer include aliphatic or alicyclic hydrocarbon compounds such as hexane, heptane, octane, cyclohexane, cyclopentane, cyclooctane and the like; toluene, xylene Or an aromatic hydrocarbon compound such as ethylbenzene; ethyl acetate, butyl acetate, amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ester compound such as ethylene glycol monobutyl ether acetate; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, n-amyl alcohol, i-amyl alcohol, tert-amyl alcohol, ethylene Alcohol compounds such as recalled monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone and cyclohexanone; dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether, di-n -Ether compounds such as butyl ether; Chlorinated hydrocarbon compounds such as chloroform, methylene chloride, carbon tetrachloride, trichloroethane, tetrachloroethane, etc .; N-methylpyrrolidone, dimethyl formamide, dimethylacetamide, ethylene carbonate, etc. can be used. These organic solvents may be used alone or in combination of two or more.

  Examples of polymerization initiators that can be used when producing the vinyl polymer include, for example, radical polymerization initiators such as persulfates, organic peroxides and hydrogen peroxide, and 4,4′-azobis (4-cyano Azo initiators such as valeric acid), 2,2'-azobis (2-amidinopropane) dihydrochloride can be used. The radical polymerization initiator may be used as a redox polymerization initiator, for example, in combination with a reducing agent such as ascorbic acid. These polymerization initiators may be used alone or in combination of two or more.

  Examples of the persulfate which is representative of the above-mentioned polymerization initiator include potassium persulfate, sodium persulfate, ammonium persulfate and the like, and as the organic peroxide, specifically, for example, benzoyl peroxide , Diacyl peroxides such as lauroyl peroxide and decanoyl peroxide, dialkyl peroxides such as t-butylcumyl peroxide and dicumyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxy Peroxy esters such as laurate, t-butylperoxybenzoate, cumene hydroperoxide, paramenthane hydroperoxide, hydroperoxides such as t-butyl hydroperoxide, etc. can be used.

  The amount of polymerization initiator used may be such that the polymerization proceeds smoothly, but should be 10% by mass or less based on the total amount of vinyl monomers used for producing the vinyl polymer (a2). Is preferred.

The glass transition temperature of the vinyl polymer is preferably in the range of −50 to 90 ° C. because the adhesion of the resulting coating film is further improved. In the present invention, the glass transition temperature (Tg) is a glass transition temperature calculated by the following formula of FOX.
Formula of FOX: 1 / Tg = W1 / Tg1 + W2 / Tg2 +.
(Tg: glass transition temperature to be determined, W1: weight fraction of component 1, Tg1: glass transition temperature of homopolymer of component 1)

  Moreover, it is preferable to form the said polysiloxane (a1) by passing through a two-step reaction process in the process of manufacturing the said composite resin (A). Specifically, a polysiloxane structure is formed by reacting a relatively low molecular weight silane compound such as phenyltrimethoxysilane with the hydrolyzable group etc. possessed by the vinyl polymer (a1), and then the reaction By reacting a substance with a condensate such as methyltrimethoxysilane or ethyltrimethoxysilane, a structure composed of polysiloxane (a1) can be formed. Thereby, the resin composition for adhesion | attachment which can form the coating film which was further excellent in durability, such as adhesiveness and a weather resistance, heat resistance, can be obtained.

  The composite resin (A) can be produced, for example, by the following steps (I) to (II).

  The step (I) is a step of polymerizing the above-mentioned vinyl monomer in the presence of the above-mentioned polymerization initiator in an organic solvent to obtain an organic solvent solution of the vinyl polymer (a2).

  The polymerization reaction is carried out, for example, by sequentially feeding or batch feeding the vinyl monomer in an organic solvent containing a polymerization initiator, and then performing stirring for about 0.5 to 24 hours at a range of 20 to 120 ° C. Is preferred.

  In the step (II), a reactive functional group such as a hydrolyzable silyl group possessed by the vinyl polymer (a2) in the organic solvent solution of the vinyl polymer (a2) and a hydrolysis possessed by the silane compound The composite resin (A) in which the vinyl polymer (a2) and the polysiloxane (a1) are bonded by advancing the reaction with a reactive silyl group or silanol group and the hydrolytic condensation reaction between the silane compounds A step of obtaining an organic solvent solution of

  Such reaction is carried out, for example, sequentially or collectively supplying the silane compound capable of forming the polysiloxane (a1) into the organic solvent solution of the vinyl polymer (a2) subsequently to the step (I). Under stirring, it is preferable to carry out in the range of 20 to 120 ° C. for about 0.5 to 24 hours.

  The step (II) is preferably further subjected to two reaction steps. Specifically, the step of reacting the hydrolyzable silyl group or silanol group possessed by the vinyl polymer (a2) with a relatively low molecular weight silane compound such as the above-mentioned phenyltrimethoxysilane, and then the reaction product And a condensation product obtained by previously condensing methyltrialkoxysilane such as methyltrimethoxysilane or ethyltrimethoxysilane and ethyltrialkoxysilane. By performing the structure formation of the polysiloxane (a1) in two steps as described above, an adhesive resin composition capable of forming a coating film excellent in durability such as adhesiveness, weather resistance, heat resistance, etc. is obtained. be able to.

  The adhesive resin composition of the present invention is one in which the composite resin (A) is dissolved or dispersed in a medium, and the medium can be used, for example, when producing the vinyl polymer. And various organic solvents listed as examples.

  The adhesive resin composition may also contain a thermosetting resin, if necessary. Examples of the thermosetting resin include vinyl resins, polyester resins, polyurethane resins, epoxy resins, epoxy ester resins, acrylic resins, phenol resins, petroleum resins, ketone resins, silicone resins, and modified resins thereof.

  Various inorganic particles such as clay mineral, metal, metal oxide, glass and the like can be used in the adhesive resin composition, if necessary. Examples of metals include gold, silver, copper, platinum, titanium, zinc, nickel, aluminum, iron, silicon, germanium, antimony, metal oxides thereof, and the like.

  The adhesive resin composition may, if necessary, be a photocatalytic compound, an inorganic pigment, a rust preventive pigment, an extender pigment, an organic pigment, a wax, a surfactant, a stabilizer, an adhesion promoter, a flow control agent, a dye, Various additives such as leveling agents, rheology control agents, ultraviolet light absorbers, antioxidants, plasticizers and the like can be used.

  The adhesive resin composition can be suitably used as a primer, an adhesive and the like because it can form a coating film excellent in adhesion to various substrates. In particular, it is useful for adhesion of a primer to a hard-to-deposition substrate and adhesion between different types of substrates, and can form a coating film excellent in weather resistance and heat resistance, so it is also very useful as an adhesive for transparent substrates.

  Examples of the substrate on which the primer is applied to form a coating film include inorganic substrates such as stainless steel, alumina, graphite and talc, metal substrates such as galvanized steel plates and cold rolled steel plates, polycarbonate, ABS, and polyolefins Etc., glass substrates, rubber substrates such as NBR, SBR, silicone rubber, etc., paper and wood substrates, fibrous substrates such as FRP, and the like.

  Moreover, as a shape of the said base material, plate shape, spherical shape, a film shape, sheet shape etc. are mentioned, for example. Moreover, you may have fine unevenness | corrugation on these base-material surfaces.

  An article having a coating of the primer can be obtained by coating and curing the primer on various substrates as described above. At that time, (1) the primer is applied directly to the substrate, (2) the primer is applied to the substrate as an undercoat paint, and then another top coat is applied to form a coating film, etc. It is possible to obtain a paint.

  Examples of the method for coating the primer agent include brush coating, roller coating, spray coating, dip coating, flow coater coating, roll coater coating, electrodeposition coating and the like.

  The drying and curing may be progressed at about 1 to 10 days under normal temperature, but from the viewpoint of rapidly curing, it may be 1 to 600 seconds at a temperature of 50 to 250 ° C. A method of heating to a certain extent is preferred.

  The film thickness of the coating film formed using the said primer can be 0.5-1,000 micrometers according to the use etc. in which a base material is used.

  Articles having a coating film formed using the primer by the method as described above include, for example, steel structures; bridges, tanks, plants, building members such as outer walls and roofs; guard rails, sound barriers, drainage grooves Civil engineering members such as: Home appliances, industrial machines, aircraft, parts of automobiles, etc .; Drive parts, exhaust parts, thermal power plant members, etc.

An article having a coating of the adhesive can be obtained by coating and curing the adhesive on various substrates as described above. At that time, (1) the adhesive is applied to the substrate by a bar coating method or a spray method, (2) an open time is provided to partially volatilize the solvent, and then the weight, the pressing device, the laminating device 80 An article can be obtained by pressing and curing while heating at ̃150 ° C. for 5 minutes or more.

  As an article which has a coat of the above-mentioned adhesives, it can be used for an application illustrated as an article which has a coat formed, for example using the above-mentioned primer.

  Next, the present invention will be specifically described by way of examples and comparative examples. In addition, the average molecular weight of resin is measured on the following GPC measurement conditions. Moreover, as a base material for evaluation, a silicon rubber sheet (JIS K6380) and the other base material used the thing by Engineering Test Service Co., Ltd.

[GPC measurement conditions]
Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were used in series connection.
"TSKgel G5000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 4000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 3000" (7.8 mm ID × 30 cm) × 1 This "TSKgel G2000" (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 4 mg / mL)
Standard sample: A calibration curve was prepared using the following monodispersed polystyrene.

(Monodispersed polystyrene)
Tosoh Corporation "TSKgel standard polystyrene A-500"
Tosoh Corporation "TSKgel standard polystyrene A-1000"
Tosoh Corporation "TSKgel standard polystyrene A-2500"
Tosoh Corporation "TSKgel standard polystyrene A-5000"
Tosoh Corporation "TSKgel standard polystyrene F-1"
Tosoh Corporation "TSKgel standard polystyrene F-2"
Tosoh Corporation "TSKgel standard polystyrene F-4"
Tosoh Corporation "TSKgel standard polystyrene F-10"
Tosoh Corporation "TSKgel standard polystyrene F-20"
Tosoh Corporation "TSKgel standard polystyrene F-40"
Tosoh Corporation "TSKgel standard polystyrene F-80"
Tosoh Corporation "TSKgel standard polystyrene F-128"
Tosoh Corporation "TSKgel standard polystyrene F-288"
Tosoh Corporation "TSKgel standard polystyrene F-550"

Synthesis Example 1: Synthesis of methyltrimethoxysilane condensate (a1′-1)
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling pipe and nitrogen gas inlet, 1,421 parts by mass of methyltrimethoxysilane (hereinafter abbreviated as "MTMS") was charged, and the temperature was raised to 60 ° C. It warmed. Then, a mixture of 0.17 parts by mass of iso-propyl acid phosphate ("Phoslex A-3" manufactured by SC Organic Chemical Co., Ltd.) and 207 parts by mass of deionized water is dropped into the reaction vessel over 5 minutes, and then 80 The mixture was stirred at a temperature of ° C for 4 hours for hydrolysis and condensation reaction.
The condensate obtained by the above hydrolysis condensation reaction is reduced in temperature at 40 to 60 ° C. and 40 to 1.3 kPa (the reduced pressure condition at the start of distillation of methanol is 40 kPa and finally it becomes 1.3 kPa) Refers to the conditions under which the pressure is reduced down to the following: Same as above) and removes methanol and water generated in the reaction process, thereby containing MTMS condensate (a1'-1) with a number average molecular weight of 1,000. 1,000 parts by mass of liquid (70% by mass of active ingredient) was obtained.
The above-mentioned effective ingredient is the value obtained by dividing the theoretical yield (parts by mass) when all the methoxy groups of silane monomers such as MTMS are condensation reacted by the actual yield (parts by mass) after the condensation reaction [methoxy of silane monomer It is calculated by the theoretical yield (mass part) / real yield after condensation reaction (mass part)] when all the groups carry out a condensation reaction.

Example 1 Production of Resin Composition for Bonding (1)
150 parts by mass of n-butanol (hereinafter abbreviated as "BuOH"), phenyltrimethoxysilane (hereinafter "PTMS") in a reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling pipe and nitrogen gas inlet 88 parts by mass, and 233 parts by mass of dimethyldimethoxysilane (hereinafter abbreviated as "DMDMS") were charged, and the temperature was raised to 80.degree.
Subsequently, 84 parts by mass of methyl methacrylate (hereinafter abbreviated as "MMA"), 16 parts by mass of butyl methacrylate (hereinafter abbreviated as "BMA") at the same temperature, and butyl acrylate (hereinafter abbreviated as "BA") ) 13 parts by mass, 7 parts by mass of 3-methacryloxypropyltrimethoxysilane (hereinafter abbreviated as "MPTS"), 12 parts by mass of BuOH and tert-butylperoxy-2-ethylhexanoate (hereinafter "TBPEH") A mixture containing 2.4 parts by mass is dropped into the reaction vessel over 4 hours, and after completion of the dropping, the mixture is further reacted at the same temperature for 20 hours to obtain a number average having a hydrolyzable silyl group. An organic solvent solution of vinyl polymer (a2-1) having a molecular weight of 10,200 was obtained.
Then, a mixture of 0.04 parts by mass of iso-propyl acid phosphate ("Phoslex A-3" manufactured by SC Organic Chemical Co., Ltd., hereinafter abbreviated as "A-3") and 94 parts by mass of deionized water is The reaction solution is added dropwise for 1 minute, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, whereby the hydrolysis of the hydrolyzable silyl group possessed by the vinyl polymer (a2-1) and the hydrolysis possessed by the PTMS and DMMS derived from polysiloxane. A liquid containing a composite resin in which a degradable silyl group and a silanol group were bonded was obtained.
Next, 398 parts by mass of the MTMS condensate (a1′-1) obtained in Synthesis Example 1 and 67 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction. The product was subjected to distillation under the same conditions as in Synthesis Example 1 to remove methanol and water formed, and then 250 parts by mass of BuOH was added, and a resin composition for adhesion having a nonvolatile content of 60.1% by mass (1 1,000 parts by mass was obtained.

Example 2 Production of Resin Composition for Bonding (2)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 150 parts by mass of BuOH, 99 parts by mass of PTMS and 263 parts by mass of DMDS were charged, and the temperature was raised to 80 ° C.
Then, a mixture containing 42 parts by mass of MMA, 8 parts by mass of BMA, 7 parts by mass of BA, 4 parts by mass of MPTS, 6 parts by mass of BuOH and 1.2 parts by mass of TBPEH at the same temperature for 5 hours into the reaction vessel It dripped and it made it react at the same temperature for 20 hours after completion | finish of dripping, and obtained the organic solvent solution of the vinyl polymer (a2-2) of the number average molecular weight 10,300 which has a hydrolysable silyl group.
Next, a mixture of 0.04 parts by mass of A-3 and 106 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group possessed by (-2) and the hydrolyzable silyl group and silanol group possessed by the PTMS and the DMMS derived from polysiloxane are bonded.
Next, 447 parts by mass of the MTMS condensate (a1'-1) obtained in Synthesis Example 1 and 76 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction. The product was subjected to distillation under the same conditions as in Synthesis Example 1 to remove methanol and water formed, and then 250 parts by mass of BuOH was added, and a resin composition for adhesion having a nonvolatile content of 60.0% by mass (2 1,000 parts by mass was obtained.

Example 3 Production of Resin Composition for Bonding (3)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 150 parts by mass of BuOH, 105 parts by mass of PTMS and 277 parts by mass of DMDS were charged, and the temperature was raised to 80 ° C.
Then, a mixture containing 21 parts by mass of MMA, 4 parts by mass of BMA, 3 parts by mass of BA, 2 parts by mass of MPTS, 3 parts by mass of BuOH and 0.6 parts by mass of TBPEH at the same temperature for 6 hours into the reaction vessel It dripped and it made it react at the same temperature for 20 hours after completion | finish of dripping, and obtained the organic solvent solution of the vinyl polymer (a2-3) of the number average molecular weight 10,000 which has a hydrolysable silyl group.
Next, a mixture of 0.04 parts by mass of A-3 and 112 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group of -3) and the hydrolyzable silyl group and silanol group of the PTMS and the polysiloxane derived from DMMS are bonded.
Next, to this solution, 472 parts by mass of the MTMS condensate (a1′-1) obtained in Synthesis Example 1 and 80 parts by mass of deionized water were added, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction. The product was subjected to distillation under the same conditions as in Synthesis Example 1 to remove methanol and water formed, and then 250 parts by mass of BuOH was added, and a resin composition for adhesion having a non-volatile content of 60.1% by mass (3 1,000 parts by mass was obtained.

Example 4 Production of Resin Composition for Bonding (4)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 150 parts by mass of BuOH, 108 parts by mass of PTMS and 286 parts by mass of DMDMS were charged and the temperature was raised to 80 ° C.
Then, a mixture containing 8 parts by mass of MMA, 2 parts by mass of BMA, 1 part by mass of BA, 1 part by mass of MPTS, 2 parts by mass of BuOH and 0.3 parts by mass of TBPEH at the same temperature for 6 hours into the reaction vessel It dripped and it made it react at the same temperature for 20 hours after completion | finish of dripping, and obtained the organic solvent solution of the vinyl polymer (a2-4) of the number average molecular weight 10,300 which has a hydrolysable silyl group.
Next, a mixture of 0.05 parts by mass of A-3 and 115 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group possessed by (4) and the hydrolyzable silyl group possessed by the PTMS and the polysiloxane derived from DMDMS and the silanol group are bonded.
Next, 487 parts by mass of the MTMS condensate (a1'-1) obtained in Synthesis Example 1 and 82 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction. The product was subjected to distillation under the same conditions as in Synthesis Example 1 to remove methanol and water formed, and then 250 parts by mass of BuOH was added, and a resin composition for adhesion having a nonvolatile content of 60.2% by mass (4 1,000 parts by mass was obtained.

Example 5 Production of Resin Composition for Bonding (5)
MMA 18 parts by weight instead of the mixture used in Example 2 containing 42 parts by weight of MMA, 8 parts by weight of BMA, 7 parts by weight of BA, 4 parts by weight of MPTS, 6 parts by weight of BuOH and 1.2 parts by weight of TBPEH , BMA 14 parts by mass, BA 7 parts by mass, acrylic acid (hereinafter abbreviated as “AA”) 1 part by mass, MPTS 2 parts by mass, BuOH 6 parts by mass and TBPEH 0.9 parts by mass. An operation was performed in the same manner as in Example 2 except for the above to obtain 1,000 parts by mass of a bonding resin composition (5) having a nonvolatile content of 60.0%.

Example 6 Production of Resin Composition for Bonding (6)
MMA 12 parts by mass instead of the mixture used in Example 2 containing 42 parts by mass of MMA, 8 parts by mass of BMA, 7 parts by mass of BA, 4 parts by mass of MPTS, 6 parts by mass of BuOH and 1.2 parts by mass of TBPEH The procedure of Example 2 is repeated except that a mixture containing 15 parts by mass of cyclohexyl methacrylate, 32 parts by mass of 2-ethylhexyl acrylate, 1 part by mass of MPTS, 6 parts by mass of BuOH and 0.6 parts by mass of TBPEH is used. As a result, 1,000 parts by mass of a bonding resin composition (6) having a nonvolatile content of 60.2% was obtained.

Example 7 Production of Resin Composition for Bonding (7)
150 parts by mass of BuOH, 133 parts by mass of diphenyldimethoxysilane (hereinafter abbreviated as "DPDMS"), and 350 parts by mass of DMDMS in a reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling pipe and nitrogen gas inlet The mixture was charged and heated to 80 ° C.
Subsequently, a mixture containing 18 parts by mass of MMA, 14 parts by mass of BMA, 7 parts by mass of BA, 1 part by mass of AA, 2 parts by mass of MPTS, 6 parts by mass of BuOH and 0.9 parts by mass of TBPEH at the same temperature The reaction solution is dropped for 5 hours and allowed to react at the same temperature for 10 hours to obtain an organic solvent solution of a vinyl polymer (a2-7) having a hydrolyzable silyl group and having a number average molecular weight of 20,000. The
Next, a mixture of 0.05 parts by mass of A-3 and 134 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 A liquid containing a composite resin in which the hydrolyzable silyl group possessed by (7) and the hydrolyzable silyl group possessed by the DDPMS and the polysiloxane derived from DMDMS and the silanol group are bonded is obtained.
Next, 309 parts by mass of the MTMS condensate (a1′-1) obtained in Synthesis Example 1 and 52 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 15 hours to cause a hydrolysis condensation reaction. The product was subjected to distillation under the same conditions as in Synthesis Example 1 to remove methanol and water formed, and then 250 parts by mass of BuOH was added, and a resin composition for adhesion having a nonvolatile content of 60.0% by mass (7 1,000 parts by mass was obtained.

Example 8 Production of Resin Composition for Bonding (8)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser and a nitrogen gas inlet, 150 parts by mass of BuOH, 249 parts by mass of PTMS and 263 parts by mass of DMDS were charged, and the temperature was raised to 80 ° C.
Subsequently, a mixture containing 18 parts by mass of MMA, 14 parts by mass of BMA, 7 parts by mass of BA, 1 part by mass of AA, 2 parts by mass of MPTS, 6 parts by mass of BuOH and 0.9 parts by mass of TBPEH at the same temperature The reaction solution is dropped for 5 hours into the mixture, and after completion of the dropping, the mixture is further reacted at the same temperature for 10 hours to obtain an organic solvent solution of a vinyl polymer (a2-8) having a hydrolyzable silyl group and a number average molecular weight of 20,100 The
Next, a mixture of 0.05 parts by mass of A-3 and 147 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group possessed by -8) and the hydrolyzable silyl group possessed by the PTMS and the DMMS derived from polysiloxane and the silanol group are bonded.
Subsequently, 76 parts by mass of 3-glycidoxypropyltrimethoxysilane, 231 parts by mass of the MTMS condensate (a1'-1) obtained in Synthesis Example 1, and 56 parts by mass of deionized water are added to this solution, Methanol and water which were produced by distilling under the same conditions as those of Synthesis Example 1 were removed by stirring at a temperature for 15 hours for hydrolysis and condensation reaction, then 250 parts by mass of BuOH was added, and the non volatile matter was 1,000 parts by mass of 60.0% by mass of the adhesive resin composition (8) were obtained.

Example 9 Production of Resin Composition for Bonding (9)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser and a nitrogen gas inlet, 150 parts by mass of BuOH, 414 parts by mass of PTMS and 263 parts by mass of DMDMS were charged and the temperature was raised to 80 ° C.
Subsequently, a mixture containing 18 parts by mass of MMA, 14 parts by mass of BMA, 7 parts by mass of BA, 1 part by mass of AA, 2 parts by mass of MPTS, 6 parts by mass of BuOH and 0.9 parts by mass of TBPEH at the same temperature The reaction solution is dropped for 6 hours, and after completion of the dropwise addition, the reaction is carried out for 10 hours at the same temperature to obtain an organic solvent solution of a vinyl polymer (a2-9) having a hydrolyzable silyl group and a number average molecular weight of 19,600. The
Next, a mixture of 0.07 parts by mass of A-3 and 192 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group of -9) and the hydrolyzable silyl group and silanol group of the PTMS and the polysiloxane derived from DMMS are bonded.
Next, 154 parts by mass of the MTMS condensate (a1'-1) obtained in Synthesis Example 1 and 26 parts by mass of deionized water were added to this solution, and the mixture was stirred for 5 hours at the same temperature to cause a hydrolysis condensation reaction. The product was subjected to distillation under the same conditions as in Synthesis Example 1 to remove methanol and water formed, and then 250 parts by mass of BuOH was added, and a resin composition for adhesion having a non-volatile content of 60.1% by mass (9 1,000 parts by mass was obtained.

Comparative Example 1: Production of Resin Composition for Adhesion (R-1)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 150 parts by mass of BuOH, 33 parts by mass of PTMS, and 88 parts by mass of DMDMS were charged and the temperature was raised to 80 ° C.
Then, at the same temperature, a mixture containing 294 parts by mass of MMA, 55 parts by mass of BMA, 46 parts by mass of BA, 25 parts by mass of MPTS, 42 parts by mass of BuOH and 8.4 parts by mass of TBPEH is introduced into the reaction vessel for 3 hours It dripped and it made it react at the same temperature for 20 hours after completion | finish of dripping, and obtained the organic solvent solution of the vinyl polymer (Ra2-1) of the number average molecular weight 11,000 which has a hydrolysable silyl group.
Next, a mixture of 0.01 part by mass of A-3 and 35 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, thereby obtaining a vinyl polymer (Ra2). There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group possessed by -1) and the hydrolyzable silyl group possessed by the PTMS and the DMMS derived from polysiloxane and the silanol group are bonded.
Subsequently, 149 parts by mass of the MTMS condensate (a1'-1) obtained in Synthesis Example 1 and 25 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction. The product was subjected to distillation under the same conditions as in Synthesis Example 1 to remove methanol and water generated, and then 250 parts by mass of BuOH was added, and a resin composition for adhesion having a nonvolatile content of 60.0% by mass (R 1,000 parts by mass of -1) were obtained.

Comparative Example 2: Production of Resin Composition for Adhesion (R-2)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 150 parts by mass of BuOH, 66 parts by mass of PTMS and 175 parts by mass of DMDS were charged, and the temperature was raised to 80 ° C.
Then, at the same temperature, a mixture containing 168 parts by mass of MMA, 31 parts by mass of BMA, 26 parts by mass of BA, 14 parts by mass of MPTS, 24 parts by mass of BuOH and 4.8 parts by mass of TBPEH is introduced into the reaction vessel for 4 hours It dripped and it made it react at the same temperature for 20 hours after completion | finish of dripping, and obtained the organic solvent solution of the vinyl polymer (Ra2-2) of the number average molecular weight 10,200 which has a hydrolysable silyl group.
Then, a mixture of 0.03 parts by mass of A-3 and 70 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, thereby obtaining a vinyl polymer (Ra2). There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group possessed by (-2) and the hydrolyzable silyl group and silanol group possessed by the PTMS and the DMMS derived from polysiloxane are bonded.
Next, 298 parts by mass of the MTMS condensate (a1'-1) obtained in Synthesis Example 1 and 50 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction. The product was subjected to distillation under the same conditions as in Synthesis Example 1 to remove methanol and water generated, and then 250 parts by mass of BuOH was added, and a resin composition for adhesion having a nonvolatile content of 60.0% by mass (R 1,000 parts by mass of 2) were obtained.

(Comparative example 3: manufacture of resin composition (R-3) for adhesion)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 150 parts by mass of BuOH, 111 parts by mass of PTMS, and 292 parts by mass of DMDS were charged, and the temperature was raised to 80 ° C.
Then, a mixture of 0.05 parts by mass of A-3 and 118 parts by mass of deionized water is added dropwise over 5 minutes at the same temperature, and the PTMS is further subjected to a hydrolysis condensation reaction by stirring for 10 hours at the same temperature. And the liquid containing the polysiloxane derived from DMDMS was obtained.
Next, 497 parts by mass of the MTMS condensate (a1'-1) obtained in Synthesis Example 1 and 84 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction. The product was subjected to distillation under the same conditions as in Synthesis Example 1 to remove methanol and water generated, and then 250 parts by mass of BuOH was added, and a resin composition for adhesion having a nonvolatile content of 60.0% by mass (R 1,000 parts by mass of -3) were obtained.

Comparative Example 4 Production of Resin Composition for Adhesion (R-4)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 150 parts by mass of BuOH, 41 parts by mass of PTMS and 263 parts by mass of DMDMS were charged and the temperature was raised to 80 ° C.
Then, a mixture containing 42 parts by mass of MMA, 8 parts by mass of BMA, 7 parts by mass of BA, 4 parts by mass of MPTS, 6 parts by mass of BuOH and 1.2 parts by mass of TBPEH at the same temperature for 5 hours into the reaction vessel It dripped and after completion | finish of dripping, it was made to react at the same temperature for 20 hours, and the organic solvent solution of the vinyl polymer (Ra2-4) of the number average molecular weight 10,400 which has a hydrolysable silyl group was obtained.
Next, a mixture of 0.04 parts by mass of A-3 and 90 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, thereby obtaining a vinyl polymer (Ra2). There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group possessed by (4) and the hydrolyzable silyl group possessed by the PTMS and the polysiloxane derived from DMDMS and the silanol group are bonded.
Next, to this solution was added 501 parts by mass of the MTMS condensate (a1'-1) obtained in Synthesis Example 1 and 85 parts by mass of deionized water, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction. The product was subjected to distillation under the same conditions as in Synthesis Example 1 to remove methanol and water generated, and then 250 parts by mass of BuOH was added, and a resin composition for adhesion having a nonvolatile content of 60.0% by mass (R 1,000 parts by mass of -4) was obtained.

(Comparative example 5: Manufacture of a resin composition (R-5) for adhesion)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 150 parts by mass of BuOH, 332 parts by mass of PTMS and 350 parts by mass of DMDMS were charged and the temperature was raised to 80 ° C.
Then, a mixture containing 42 parts by mass of MMA, 8 parts by mass of BMA, 7 parts by mass of BA, 4 parts by mass of MPTS, 6 parts by mass of BuOH and 1.2 parts by mass of TBPEH at the same temperature for 6 hours into the reaction vessel It dripped and it made it react at the same temperature for 20 hours after completion | finish of dripping, and obtained the organic solvent solution of the vinyl polymer (Ra2-5) of the number average molecular weight 10,000 which has a hydrolysable silyl group.
Next, a mixture of 0.07 parts by mass of A-3 and 195 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, thereby obtaining a vinyl polymer (Ra2). There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group possessed by (-5) and the hydrolyzable silyl group and silanol group possessed by the PTMS and the polysiloxane derived from DMDS are bonded.
Subsequently, 153 parts by mass of 3-glycidoxypropyltrimethoxysilane and 35 parts by mass of deionized water were added to this solution, and the mixture was stirred for 10 hours at the same temperature for hydrolysis and condensation reaction, as in Synthesis Example 1. Of methanol and water generated by distillation under the following conditions, and then adding 250 parts by mass of BuOH, and 1,000 parts by mass of the adhesive resin composition (R-5) having a nonvolatile content of 60.0% by mass. I got a part.

(Comparative example 6: manufacture of resin composition (R-6) for adhesion)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 690 parts by mass of BuOH were charged and the temperature was raised to 80 ° C.
Then, a mixture containing 193 parts by mass of MMA, 36 parts by mass of BMA, 30 parts by mass of BA, 17 parts by mass of MPTS, 28 parts by mass of BuOH and 5.5 parts by mass of TBPEH at the same temperature for 3 hours into the reaction vessel It dripped and made it react at the same temperature for 20 hours after completion | finish of dripping, and the organic solvent solution of the vinyl polymer (Ra2-6) of a number average molecular weight 10,300 was obtained.
Subsequently, 808 parts by mass of the adhesive resin composition (R-3) obtained in Comparative Example 3 and 192 parts by mass of an organic solvent solution of a vinyl polymer (Ra2-6) having a nonvolatile content of 28.0% by mass are mixed. By stirring at the same temperature for 1 hour, 1,000 parts by mass of a bonding resin composition (R-6) having a non-volatile content of 53.8% by mass was obtained.

[Evaluation of storage stability]
The storage stability of the adhesive resin composition obtained above was evaluated at a viscosity ratio with an initial viscosity as a denominator, with the viscosity (so-called viscosity over time) of what was stored at 50 ° C. for 30 days as a molecule. The viscosity was measured at 25 ° C. using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Moreover, the storage of the sample was performed by putting the obtained coating agent for metals in a glass tube and allowing it to stand for 30 days under an environment of 50 ° C. A resin composition having a viscosity ratio of 0.9 or more and 1.1 or less and a very excellent storage stability, as the viscosity ratio is closer to 1 means that the storage stability is more excellent. It was determined to be a thing.

[Preparation of cured film for evaluation]
The resin composition for bonding obtained above was treated with a soft glass plate (JIS R 3202), a chromate-treated aluminum plate (JIS H 4000: A5052P), a polyethylene terephthalate plate (Lumirror T-60 manufactured by Toray Industries, Inc.), an aluminum plate ( JIS H 4000: A1050P), a polypropylene plate (JIS K 6921), a polyvinyl chloride plate (JIS K 6745), and a silicone rubber sheet are coated to a thickness of 30 μm on the cured coating film. The coated film was dried for 15 minutes in an environment of 120 ° C. to obtain a cured coating for evaluation.

[Measurement of total light transmittance]
About the cured coating film for evaluation on the glass base material obtained above, the measurement of the total light transmittance was performed by Nippon Denshoku Industries Co., Ltd. make haze meter NDH-5000.

[Evaluation of coating film appearance]
The cured coating films for evaluation on the glass plate and the chromate-treated aluminum plate obtained above were visually observed, and the coating film appearance was evaluated according to the following criteria.
○: No occurrence of cracking and whitening was observed.
Δ: Some occurrence of cracking or whitening is observed.
X: Occurrence of cracking or whitening is observed.

[Evaluation of adhesion]
About the cured coating film for evaluation on each base material obtained above, it measured based on the JIS K-5600 cross-cut test method. A cut of 1 mm in width is made with a cutter on the cured coating film, the number of grids is 100, a cellophane tape is pasted so as to cover all grids, and the grids are peeled off and adhered Were counted and evaluated according to the following criteria.
○: There is no peeling.
Δ: The area of peeling is 1 to 64% of the total grid area.
×: Peeling area is 65% or more of the total grid area.

[Evaluation of heat resistance (appearance)]
The cured coating film for evaluation on the glass plate and the chromate-treated aluminum plate obtained above was allowed to stand in a dryer at 300 ° C. for 24 hours, and then the appearance after taking it out from the dryer was visually observed. It evaluated by the standard.
○: No occurrence of cracks observed.
Δ: Some occurrence of cracks is observed.
X: Generation of a crack is recognized.

[Evaluation of heat resistance (adhesiveness)]
The cured coating film for evaluation on the glass plate and the chromate-treated aluminum plate obtained above was allowed to stand in a dryer at 300 ° C. for 24 hours and then removed from the dryer and allowed to stand for 1 hour. After that, cut a 1 mm width with a cutter on the coating and cut the number of grids to 100, paste the cellophane tape so as to cover all grids, remove it quickly, and adhere and leave the grids Were counted and evaluated according to the following criteria.
○: There is no peeling.
Δ: Peeling area is 1 to 64% of total grid area.
×: Peeling area is 65% or more of the total grid area.

[Evaluation of weatherability (appearance)]
With regard to the cured film for evaluation on the chromate-treated aluminum plate obtained above, a Dew panel light weather meter (manufactured by Suga Test Instruments Co., Ltd., at the time of light irradiation: 30 W / m ² , 70 ° C .; wet: 90% or more of humidity) After 1,000 hours of exposure at 50 ° C., light irradiation / wet cycle = 8 hours / 4 hours), the coating film was visually observed, and the coating appearance was evaluated based on the following criteria.
○: No occurrence of cracks observed.
Δ: Some occurrence of cracks is observed.
X: Generation of a crack is recognized.

[Evaluation of weather resistance (gloss retention)]
The specular reflectance (gloss value) (%) of the cured coating film for evaluation on the chromate-treated aluminum plate immediately after preparation obtained as described above, and the cured coating film were measured using a de-panel optical weather meter (manufactured by Suga Test Instruments Co., Ltd.) At the time of light irradiation: 30 W / m 2, 70 ° C .; at the time of humidity: 90% or more of humidity, 50 ° C., light irradiation / wet cycle = 8 hours / 4 hours) specular reflectance of coating film after 1,000 hours exposure Retention rate (gloss retention rate) (% glossiness) of the (Gloss value) (%) relative to the specular reflectance (gloss value) of the cured coating film before exposure [(specular reflectance of coating after exposure) / (exposure Specular reflectance of previous cured coating film)]. The larger the retention value, the better the weather resistance.

[Evaluation of peel strength]
After coating 1 g of the adhesive resin composition obtained above on the center of one substrate, overlay the other substrate so as to form a cross, and press-bond at 120 ° C. for 10 minutes for evaluation test pieces I got
The peel strength of the test piece for evaluation was evaluated by the precision universal testing machine AG-I / XR (manufactured by Shimadzu Corporation) under the following conditions.
Sample shape: 25mm x 100mm x 5mm
Tensile speed: 1 mm / min Measurement atmosphere: 23 ° C, 50% RH

  Tables 1 to 4 show the evaluation results of Examples 1 to 9 and Comparative Examples 1 to 6 described above.

  The adhesive resin compositions of Examples 1 to 9 are excellent in storage stability, and from these adhesive resin compositions, they are excellent in various coating film properties such as appearance, adhesiveness, heat resistance, and weather resistance. It was confirmed that a cured coating was obtained. Moreover, it was confirmed that these resin compositions for adhesion are excellent in the adhesiveness between dissimilar substrates.

  Comparative Examples 1 and 2 are examples in which the polysiloxane (a1) in the composite resin (A) is lower than the lower limit of 75% by mass of the present invention, but the heat resistance of the resulting coated film is insufficient. It was confirmed that the adhesion between dissimilar substrates was poor.

  Although Comparative Example 3 is an example which does not contain a polymer (a2), it was confirmed that the storage stability is insufficient and that the coating film formation is insufficient.

  Comparative Example 4 is an example in which the structural unit (U1) in the polysiloxane (a1) is less than 10% by mass, which is the lower limit of the present invention, but storage stability, coating film appearance, adhesiveness, and heat resistance It was confirmed that the adhesion between the different substrates was poor.

  Although the comparative example 5 is an example which does not have a structural unit (U2) in polysiloxane (a1), it was confirmed that the weather resistance of the coating film obtained is inadequate.

  Comparative Example 6 is an example in which a polysiloxane solution and a vinyl polymer solution were blended, but storage stability, film formation was insufficient, and it was confirmed that adhesion between different types of substrates was poor.

Claims (5)

The polysiloxane (a1) having the structural unit (U1) represented by the general formula (1) or (2) and the structural unit (U2) represented by the general formula (3) and the polymer (a2) are generally An adhesive resin composition in which a composite resin (A) bonded by a bond represented by the formula (4) is dissolved or dispersed in a medium, and the polysiloxane (a1) in the composite resin (A) And the structural unit (U1) in the polysiloxane (a1) is 10 to 55% by mass.

(R ¹ in the general formulas (1) and (2) represents an aromatic hydrocarbon substituent, and R ² represents an aromatic hydrocarbon substituent or an alkyl group.)

(R ³ in general formula (3) represents a methyl group or an ethyl group.)

  The adhesive resin composition according to claim 1, wherein the structural unit (U1) is a structural unit derived from phenyltrimethoxysilane or diphenyldimethoxysilane.   A primer comprising the resin composition for adhesion according to claim 1 or 2.   An adhesive comprising the adhesive resin composition according to claim 1 or 2.   An article comprising the coating of the primer according to claim 3 or the coating of the adhesive according to claim 4.