WO2013172264A1

WO2013172264A1 - Copolymer composition for screen printing

Info

Publication number: WO2013172264A1
Application number: PCT/JP2013/063159
Authority: WO
Inventors: 斎藤　純治; 飯田　健二; 浩太郎朝比奈
Original assignee: 三井化学株式会社
Priority date: 2012-05-18
Filing date: 2013-05-10
Publication date: 2013-11-21
Also published as: TW201400509A; CN104271685A; KR20150005993A; JP5826111B2; JP2013241509A

Abstract

The present invention addresses the problem of providing a copolymer composition for screen printing, which is suitable for an adhesive for touch panels, said adhesive requiring a short time for bonding a substrate and being free from curing unevenness. The present invention relates to a copolymer composition for screen printing, which is characterized by containing an ethylene/α-olefin/non-conjugated polyene random copolymer (A) that satisfies the conditions (a)-(c) described below and contains a constituent unit [i] derived from ethylene, a constituent unit [ii] derived from an α-olefin having 3-20 carbon atoms and a constituent unit [iii] derived from a specific non-conjugated polyene. (a) The molar ratio of the ethylene unit [i] to the α-olefin unit [ii] ([i]/[ii]) is from 35/65 to 95/5. (b) The iodine number is within the range of 0.5-50. (c) The limiting viscosity [η] as measured in a decalin solution at 135°C is within the range of 0.01-5.0 (dl/g).

Description

Copolymer composition for screen printing

The present invention relates to a copolymer composition for screen printing excellent in molding processability, a laminate using the copolymer composition, and an application thereof.

In recent years, the use of various electronic devices such as an ATM using a touch panel, a ticketing machine, a car navigation system, a portable game machine, a mobile phone (smart phone), and a tablet terminal is increasing. Such touch panels have different principles such as a resistive film type, a capacitance type, an optical type, and an ultrasonic type, and a method corresponding to each application is adopted and used. Each type of touch panel has a structure in which a liquid crystal panel substrate and a transparent substrate made of glass or resin are bonded together, and an adhesive having transparency is used as an adhesive for bonding and fixing them. .

As such an adhesive, a pressure-sensitive adhesive tape is usually used, but the pressure-sensitive adhesive tape has poor reworkability, and the portion remaining after cutting the pressure-sensitive adhesive tape has to be discarded, so that the yield is poor, or the adhesion is poor. There are problems such as inferior step following performance when there is a step on the surface.

In order to solve these problems, liquid adhesives are also used. As the liquid curable resin, an epoxy resin or an acrylic resin is generally used. Examples of the acrylic resin include (meth) acrylic acid alkyl ester monomer having 1 to 18 carbon atoms, a copolymerizable monomer containing a hydroxyl group, and a copolymer of a dialkyl-substituted acrylamide monomer and a crosslinking agent. Use of an optical pressure-sensitive adhesive composition (Patent Document 1: Japanese Patent Application Laid-Open No. 2011-195651), intramolecular such as (meth) acrylic polymer, dicyclopentanyl (meth) acrylate, and octyl mercaptan It has been proposed to use an adhesive made of a photocurable composition and a compound having a mercapto group (Patent Document 2: JP 2012-41499 A). When these are used, it is possible to solve the above problems when using an adhesive tape, but on the other hand, the processing time of the process of applying the optimal pattern to the substrate with a dispenser and then bonding the substrate is long. There's a problem. Further, in the case of curing with UV, there is also a problem that there is a curing unevenness in which a portion that is not exposed to light does not cure.

On the other hand, as an adhesive for a touch panel or the like, for example, an adhesive composition containing a resin component made of polyamide elastomer, polyurethane elastomer and styrene-isobutylene-styrene copolymer is used (Patent Document 3: JP 2010-168510 A). Gazette), a pressure-sensitive adhesive obtained by curing an active energy ray-curable composition containing at least a urethane polymer having a hydroxyl group and / or a carboxyl group in a molecule and a urethane polymer having an ethylenically unsaturated group in the molecule. (Patent Document 4: JP2011-111572A), a polyoxyalkylene polymer having an alkenyl group in the molecule, a compound having less than 2 to 5 hydrosilyl groups in the molecule, and Composition comprising hydrosilylation catalyst A cured product is used (Patent Document 5: JP 2010-97070 A), or an adhesive composition excellent in screen printability includes chloroprene rubber, SEBS, phenol resin, amino group-containing coupling agent, and an organic solvent. A composition containing it (Patent Document 6: Japanese Patent Application Laid-Open No. 2004-143219) has been proposed.

However, the pressure-sensitive adhesive sheet has a yield problem as in the above-mentioned pressure-sensitive adhesive tape. Moreover, in the screen printing method disclosed in Patent Document 6, a solvent drying step is essential, and there is a problem that processing time becomes long.

JP 2011-195651 A JP 2012-41499 A JP 2010-168510 A JP 2011-111152 A JP 2010-97070 A JP 2004-143219 A

The present invention is intended to solve the problems associated with the prior art as described above, and is a copolymer composition for screen printing suitable for an adhesive for a touch panel having a short substrate bonding time and no curing unevenness. The purpose is to provide.

The present invention includes at least
(A) a structural unit [i] satisfying the following requirements (a) to (c) and derived from ethylene, a structural unit [ii] derived from an α-olefin having 3 to 20 carbon atoms, An ethylene / α-olefin / nonconjugated polyene random copolymer (A) containing a structural unit [iii] derived from at least one nonconjugated polyene selected from the formulas [I] and [II] The present invention relates to a copolymer composition for screen printing.

(A) The molar ratio of ethylene unit [i] / α-olefin unit [ii] ([i] / [ii]) is 35/65 to 95/5,
(B) the iodine value is in the range of 0.5-50,
(C) the intrinsic viscosity [η] measured in a decalin solution at 135 ° C. is in the range of 0.01 to 5.0 (dl / g);

(In the formula [I], n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. is there).

(In the formula [II], R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).

The copolymer composition for screen printing of the present invention is a resin composition for a touch panel that has a short bonding time and no unevenness of curing by directly applying to the surface of a substrate using a screen printing apparatus as an adhesive. Can be obtained.

<Ethylene / α-olefin / non-conjugated polyene random copolymer (A)>
The ethylene / α-olefin / non-conjugated polyene random copolymer (A) contained in the screen-printing copolymer composition of the present invention (hereinafter sometimes referred to simply as copolymer (A) in the present invention). . ] Satisfies the requirements (a) to (c) and is derived from ethylene, a structural unit [ii] derived from an α-olefin having 3 to 20 carbon atoms, and a general formula [ A structural unit [iii] derived from at least one non-conjugated polyene selected from I] and [II].

The copolymer (A) according to the present invention is not limited to structural isomers such as trans isomers and cis isomers as long as the effects of the present invention are exhibited.

(Α-olefin)
Specific examples of the α-olefin having 3 to 20 carbon atoms forming the structural unit [ii] derived from the α-olefin having 3 to 20 carbon atoms constituting the copolymer (A) according to the present invention include: Is propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1- Examples include tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicocene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, and the like. Among these, α-olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene, 1-octene and the like are particularly preferable.

These α-olefins may be used alone or in combination of two or more.

(Non-conjugated polyene)
The non-conjugated polyene forming the structural unit [iii] derived from the non-conjugated polyene constituting the copolymer (A) according to the present invention is a terminal vinyl group-containing norbornene compound, and the above general formulas [I] and [II] ] At least one selected from the group consisting of

In the general formula [I], n is an integer of 0 to 10, preferably an integer of 0 to 5. R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. , T-butyl group, n-pentyl group, isopentyl group, t-pentyl group, neopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group and the like. R ¹ is preferably a hydrogen atom, a methyl group or an ethyl group. R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and specific examples of the alkyl group include alkyl groups having 1 to 5 carbon atoms among the specific examples of R ¹ described above. R ² is preferably a hydrogen atom, a methyl group or an ethyl group.

In the general formula [II], R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and specific examples of the alkyl group include the same alkyl groups as those described above for R ¹ .

Examples of the norbornene compound represented by the general formula [I] or [II] include, for example, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- ( 3-butenyl) -2-norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (1-methyl-3-butenyl) -2 -Norbornene, 5- (5-hexenyl) -2-norbornene, 5- (5-heptenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2,3- Dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl-5-hexenyl) -2-norbornene, 5- (3,4-dimethyl-4-pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) -2-norbo Nene, 5- (2-methyl-6-heptenyl) -2-norbornene, 5- (1,2-dimethyl-5-hexesyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2- Examples include norbornene and 5- (1,2,3-trimethyl-4-pentenyl) -2-norbornene. Among these, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) ) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (5-heptenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (7-octenyl)- 2-norbornene is preferred.

These non-conjugated polyenes can be used alone or in combination of two or more.

In the present invention, as the non-conjugated polyene, the following non-conjugated polyene can be used in combination with the norbornene compound as long as the target physical properties of the present invention are not impaired.

Examples of such non-conjugated polyenes include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5 -Chain non-conjugated dienes such as dimethyl-1,4-hexadiene and 7-methyl-1,6-octadiene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene Cyclic non-conjugated dienes such as -2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, dicyclopentadiene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene- And trienes such as 5-norbornene and 2-propenyl-2,2-norbornadiene.

The non-conjugated polyene, which is an optional component, is usually 50 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less, based on 100 mol% of the non-conjugated polyene containing the norbornene compound used in the present invention. More preferably, it is 20 mol% or less, and particularly preferably 10 mol% or less.

(Requirement a)
The copolymer (A) according to the present invention has a molar ratio ([i] / [ii]) of the structural unit [i] derived from ethylene and the structural unit [ii] derived from α-olefin of 35 / 65 to 95/5, preferably 40/60 to 90/10, more preferably 45/55 to 85/15. When the molar ratio is within the above range, a copolymer composition for screen printing having excellent light transmittance (light transmittance) can be obtained.

The composition of the copolymer (A) can be measured using, for example, ¹³ C-NMR.

(Requirement b)
The copolymer (A) according to the present invention has an iodine value of 0.5 to 50 (g / 100 g), preferably 1 to 40 (g / 100 g), more preferably 5 to 30 (g / 100 g). Is in range. When the iodine value is within the above range, a copolymer composition for screen printing having an excellent curing rate can be obtained. An iodine value exceeding 50 is not preferable because it is disadvantageous in terms of cost.

(Requirement c)
The copolymer (A) according to the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.01 to 5.0 (dl / g), preferably 0.01 to 2.0 ( dl / g), more preferably in the range of 0.03 to 1.0 (dl / g).

When the intrinsic viscosity [η] is within the above range, a copolymer composition for screen printing having excellent processability and printability can be obtained.

In addition, when it is out of the range of the intrinsic viscosity [η], it is necessary to add a large amount of a plasticizer or a solvent in order to use it in a liquid state, and the adhesive may be deteriorated. In addition, the solvent may volatilize, causing bubbles and cloudiness.

The copolymer (A) according to the present invention is preferably in a liquid form.

The content of the non-conjugated polyene in the copolymer (A) according to the present invention is not particularly limited as long as the iodine value is satisfied, but preferably, 0.1% in 100 mol% of the copolymer (A). 05 to 8 mol%, more preferably 0.1 to 6 mol%, still more preferably 0.5 to 5 mol%.

The copolymer (A) according to the present invention preferably satisfies the following requirement (d) or (e) in addition to the above requirements (a) to (c), and all of the requirements (a) to (e) It is more preferable to satisfy.

(Requirement d)
The number average molecular weight (Mn) of the copolymer (A) according to the present invention measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 100 to 10,000, more preferably 500 to 5,000. The molecular weight distribution (Mw / Mn) is not particularly limited, but is preferably 1 to 200, more preferably 1.5 to 150. When the molecular weight distribution (Mw / Mn) is within the above range, a copolymer composition for screen printing having excellent flexibility can be obtained.

(Requirement e)
The viscosity of the copolymer (A) according to the present invention is not particularly limited, but is preferably 0.01 to 2,000 (Pa · s), more preferably 0.01 to 1,000 (Pa · s). It is. It is preferable for the viscosity to be in the above-mentioned range since a screen-printing copolymer composition having more excellent printability can be obtained.

[Method for Producing Copolymer (A)]
The copolymer (A) according to the present invention can be produced by a polymer production process (Industry Research Council, Inc., pages 309 to 330), or JP-A-9-71617, JP-A-9-71618, 9-208615, JP-A-10-67823, JP-A-10-67824, JP-A-10-110054, and the like, which can be prepared by a conventionally known method. However, the copolymer of the present invention is more preferably produced, for example, by the following production method.

The copolymer (A) according to the present invention is composed mainly of a vanadium compound represented by the following general formula (III-a) or the following general formula (III-b) and an organoaluminum compound represented by the following general formula (IV). In the presence of a catalyst contained as a polymerization temperature of 30 to 60 ° C., particularly preferably 30 to 59 ° C., a polymerization pressure of 0.4 to 5.0 MPa, particularly preferably 0.5 to 4.0 MPa, non-conjugated polyene and ethylene Random copolymerization of ethylene, an α-olefin having 3 to 20 carbon atoms, and a nonconjugated polyene under the condition of a molar ratio of supply amount to (nonconjugated polyene / ethylene) of 0.01 to 0.2 Is obtained. The copolymerization is preferably carried out in a hydrocarbon medium.

[Vanadium compounds]
The soluble vanadium compound according to the present invention is a component that is soluble in the hydrocarbon medium of the polymerization reaction system, specifically,
VO (OR) _a X _b (III-a) or V (OR) _c X _d (III-b)
(Wherein R is a hydrocarbon group, 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4)
The vanadium compound represented by these, or these electron donor adducts can be mentioned as a representative example.

More specifically, VOCl ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ Cl, VO (O-iso-C ₃ H ₇ ) Cl ₂ , VO (On-C ₄ H ₉ ) Cl ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₃ , VCl ₄ , VOCl ₃ , VO (On-C ₄ H ₉ ) ₃ , VCl ₃ .2OC ₆ H ₁₂ OH, etc. be able to.

Further, as the catalyst used in the copolymerization, a so-called metallocene catalyst, for example, a metallocene catalyst described in JP-A-9-40586 may be used. Further, as the catalyst used in the above copolymerization, a nonmetallocene catalyst such as a transition metal complex catalyst described in WO2006 / 121086 can also be used.

[Organic aluminum compound]
The organoaluminum compound according to the present invention is a compound represented by the following general formula (IV).

_{_{R 'm AlX' 3-m}} ··· (IV)
(In the formula, R ′ is a hydrocarbon group, X ′ is a halogen atom, and m is 1 to 3.)
Specific examples of the organoaluminum compound according to the present invention include trialkylaluminums such as triethylaluminum, tributylaluminum, and triisopropylaluminum; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; ethylaluminum sesquiethoxide, Alkylaluminum sesquialkoxides such as butylaluminum sesquibutoxide; partially alkoxylated alkylaluminums having an average composition represented by R ¹ _0.5 Al (OR ¹ ) _0.5 ; diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, etc. Dialkylaluminum halides; ethylaluminum sesquichloride, butylaluminum sesquik Alkyl aluminum sesquihalides such as Lido, ethylaluminum sesquibromide, partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; diethylaluminum hydride, dibutylaluminum hydride Partially hydrogenated alkylaluminums such as dialkylaluminum hydrides such as diethylaluminum hydride, ethylaluminum dihydride, propylaluminum dihydride, etc .; moieties such as ethylaluminum ethoxy chloride, butylaluminum butoxycyclide, ethylaluminum ethoxybromide Alkoxylated and halogenated alkylaluminum Can be mentioned.

In the present invention, among the above compound (III-a), a soluble vanadium compound represented by VOCl ₃ and among the above compound (IV), Al (OC ₂ H ₅ ) ₂ Cl / Al ₂ (OC ₂ H ₅ ) ₃ blend of Cl ₃ (blend ratio of 1/5 or higher) when using as a catalyst component, Soxhlet extraction (solvent: boiling xylene, extraction time: 3 hours, mesh: 325) after the insoluble matter is 1% or less Since a certain copolymer (A) is obtained, it is preferable.

Further, as the catalyst used in the copolymerization, a so-called metallocene catalyst, for example, a metallocene catalyst described in JP-A-9-40586 may be used.

The copolymer (A) according to the present invention may be graft-modified with a polar monomer such as an unsaturated carboxylic acid or a derivative thereof (such as an acid anhydride or ester).

Specific examples of such unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, and bicyclo (2,2,1) hept-2-ene. -5,6-dicarboxylic acid and the like. Specific examples of unsaturated carboxylic acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo (2,2,1) hept-2-ene-5,6- And dicarboxylic acid anhydride. Among these, maleic anhydride is preferable.

Specific examples of the unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, dimethyl maleate, monomethyl maleate, dimethyl fumarate, dimethyl itaconate, diethyl citraconic acid, tetrahydro Examples thereof include dimethyl phthalate and dimethyl bicyclo (2,2,1) hept-2-ene-5,6-dicarboxylate. Among these, methyl acrylate and ethyl acrylate are preferable.

The above-mentioned graft modifiers (graft monomers) such as unsaturated carboxylic acids are used singly or in combination of two or more, but in any case per 100 g of the copolymer (A) before graft modification described above, The graft amount is preferably 0.1 mol or less. When the graft amount is in the above range, a copolymer composition for screen printing having excellent adhesion can be obtained.

The graft-modified copolymer (A) can be obtained by reacting the above-mentioned unmodified copolymer (A) with an unsaturated carboxylic acid or a derivative thereof in the presence of a radical initiator. This grafting reaction can be performed as a solution or in a molten state. When the graft reaction is performed in a molten state, it is most efficient and preferable to perform it continuously in an extruder.

Specific examples of radical initiators used in the grafting reaction include dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, and t-butyl. Cumyl peroxide, di-t-amyl peroxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxin) hexyne-3, 2,5-dimethyl-2,5 Dialkyl such as -di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene Peroxides: t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxymaleic acid, t-butyl peroxyneodecanoate, t-butyl per Oxybenzoate , Peroxy esters di -t- butyl peroxy phthalate; ketone peroxides such as di-cyclohexanone peroxide; and mixtures thereof and the like. Of these, organic peroxides having a half-life of 1 minute in the range of 130 to 200 ° C. are preferred. Dicumyl peroxide, di-t-butyl peroxide, di-t--butylperoxy-3,3 Organic peroxides such as 1,5-trimethylcyclohexane, t-butylcumyl peroxide, di-t- amyl peroxide and t-butyl hydroperoxide are preferred.

In addition, as polar monomers other than unsaturated carboxylic acids or derivatives thereof (for example, acid anhydrides and esters), a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, Aromatic vinyl compounds, vinyl ester compounds, vinyl chloride and the like can be mentioned.

[Copolymer composition for screen printing]
The copolymer composition for screen printing of the present invention is a copolymer composition comprising the ethylene / α-olefin / non-conjugated polyene random copolymer (A).

The copolymer composition for screen printing of the present invention preferably has a viscosity at 25 ° C. of 0.1 to 100 Pa · s, more preferably 0.5 to 50 Pa · s.

The screen-printing copolymer composition of the present invention preferably has a cure shrinkage of 5% or less, preferably 4.0% or less, more preferably 3.0% or less.

The screen-printing copolymer composition of the present invention preferably has a refractive index in the range of 1.45 to 1.52, preferably 1.47 to 1.52.

The copolymer composition for screen printing of the present invention can be suitably used as an adhesive for touch panels.

In addition to the ethylene / α-olefin / non-conjugated polyene random copolymer (A), the copolymer composition for screen printing of the present invention comprises a hydrosilyl group-containing compound (B) or a molecular chain at one end. Double bonds in the molecule such as α-olefins (c1) having 6 to 3000 carbon atoms having double bonds and diolefins (c2) having 6 to 3000 carbon atoms having double bonds at both ends of the molecular chain. A compound (C) having a carbon number of 7 or more and a number average molecular weight of 2000 or less, a catalyst used in a hydrosilylation reaction, a reaction inhibitor, a silane coupling agent, a plasticizer, a stable compound An agent, an antifoaming agent (X), and the like may be included.

When the hydrosilyl group-containing compound (B) is included as the screen printing copolymer composition of the present invention, a composition having excellent adhesion and flexibility can be obtained.

When the copolymer composition for screen printing of the present invention contains the compound (C) having a double bond in the molecule, the curing rate is further increased, and a composition excellent in adhesion and flexibility can be obtained. .

When the terpene resin (D) is included as the screen printing copolymer composition of the present invention, a composition excellent in processability upon curing can be obtained.

When the screen-printing copolymer composition of the present invention has a defoaming means in the screen printing process, good printing characteristics can be obtained.

When the anti-foaming agent is included as the screen printing copolymer composition of the present invention, when the plate is released after the screen printing copolymer composition of the present invention is coated on a substrate by screen printing, Foaming due to air entering between the mesh and the liquid can be suppressed, and the loss of work time until the bonding process is small.

[Hydrosilyl group-containing compound (B)]
Hydrosilyl group-containing compound (B) according to the present invention [hereinafter referred to simply as compound (B) or SiH group-containing compound in the present invention. ] Acts as a crosslinking agent that reacts with the copolymer (A) when blended with the copolymer (A). The compound (B) according to the present invention is not particularly limited in its molecular structure as long as it contains at least 2, preferably 3 or more, hydrogen atoms directly bonded to silicon atoms, that is, SiH groups. Any conventionally manufactured resinous material such as a linear, annular, branched structure or three-dimensional network structure can be used.

When the copolymer composition for screen printing of the present invention contains the hydrosilyl group-containing compound (B), it is usually 0.1 to 100 parts by weight, preferably 100 parts by weight, preferably 100 parts by weight of the copolymer (A). It is used in a proportion of 0.1 to 75 parts by weight, more preferably 0.1 to 50 parts by weight, still more preferably 0.2 to 30 parts by weight, and particularly preferably 0.2 to 20 parts by weight.

Within the above range, a copolymer composition for screen printing having an excellent curing speed can be obtained. On the other hand, when the compound (B) is used in a proportion exceeding 100 parts by weight, it may be disadvantageous in terms of cost.

The compound (B) according to the present invention is usually represented by the following general formula [V].
R ⁴ _b H _c SiO _{(4-bc) / 2} ... [V]
The compound represented by these can be used.

In the general formula [V], R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, excluding an aliphatic unsaturated bond. In addition to the alkyl group exemplified for R ¹ , a phenyl group and a halogen-substituted alkyl group such as a trifluoropropyl group can be exemplified. Of these, a methyl group, an ethyl group, a propyl group, a phenyl group, and a trifluoropropyl group are preferable, and a methyl group and a phenyl group are particularly preferable.

Further, b is 0 ≦ b <3, preferably 0.6 <b <2.2, particularly preferably 1.5 ≦ b ≦ 2, and c is 0 <c ≦ 3, preferably 0.002. ≦ c <2, particularly preferably 0.01 ≦ c ≦ 1, and b + c is 0 <b + c ≦ 3, preferably 1.5 <b + c ≦ 2.7.

The compound (B) according to the present invention is an organohydrogenpolysiloxane having preferably 2 to 1000, particularly preferably 2 to 300, and most preferably 2 to 200 silicon atoms in one molecule. For example, 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyltetracyclosiloxane, siloxane oligomer such as 1,3,5,7,8-pentamethylpentacyclosiloxane; Trimethylsiloxy group-blocked methyl hydrogen polysiloxane, both ends of the chain trimethylsiloxy group-blocked dimethylsiloxane / methyl hydrogen siloxane copolymer, molecular chain both ends silanol group-blocked methyl hydrogen polysiloxane, molecular chain both ends silanol Block-capped dimethylsiloxane / methylhydrogensiloxane copolymer Le hydrogen siloxy group-blocked dimethylpolysiloxane with both molecular chain terminals with dimethylhydrogensiloxy groups methylhydrogenpolysiloxane capped at both molecular chain terminals blocked with dimethylhydrogensiloxy groups dimethylsiloxane-methylhydrogensiloxane copolymer, R ⁴ ₂ (H) SiO _1/2 unit and SiO _4/2 unit, optionally R ⁴ ₃ SiO _1/2 unit, R ⁴ ₂ SiO _2/2 unit, R ⁴ (H) SiO _2/2 unit, ( H) Silicone resins which can contain SiO _3/2 or R ⁴ SiO _3/2 units.

Examples of the methyl hydrogen polysiloxane blocked with trimethylsiloxy groups at both ends of the molecular chain include, for example, a compound represented by the following general formula [VI], and further a part or all of the methyl groups in the following general formula [VI] are ethyl groups, Examples include compounds substituted with a propyl group, a phenyl group, a trifluoropropyl group, and the like.
(CH ₃ ) ₃ SiO — (— SiH (CH ₃ ) —O—) _d —Si (CH ₃ ) ₃ ... [VI]
[D in the formula is an integer of 2 or more. ]

Examples of the dimethylsiloxane / methylhydrogensiloxane copolymer blocked with trimethylsiloxy groups at both ends of the molecular chain include compounds represented by the following general formula [VII], and some or all of the methyl groups in the following general formula [VII] And a compound substituted with a group, a propyl group, a phenyl group, a trifluoropropyl group, and the like.
(CH ₃ ) ₃ SiO — (— Si (CH ₃ ) ₂ —O—) _e — (— SiH (CH ₃ ) —O—) _f —Si (CH ₃ ) ₃ ... [VII]
[In the formula, e is an integer of 1 or more, and f is an integer of 2 or more. ]

Examples of the methyl hydrogen polysiloxane blocked with silanol groups at both ends of the molecular chain include, for example, a compound represented by the following general formula [VIII], and further a part or all of the methyl group in the following general formula [VIII] is an ethyl group, a propyl group, And compounds substituted with a phenyl group, a trifluoropropyl group, and the like.
_{_{HOSi (CH 3) 2 O -}} (- SiH (CH 3) -O-) 2 -Si (CH 3) 2 OH ··· [VIII]

Examples of the dimethylsiloxane / methylhydrogensiloxane copolymer blocked with silanol groups at both ends of the molecular chain include, for example, a compound represented by the following general formula [IX], and further a part or all of the methyl group in the following general formula [IX]. And compounds substituted with an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group, and the like.
_{_{HOSi (CH 3) 2 O -}} (- Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) f -Si (CH 3) 2 OH ··· [IX]
[In the formula, e is an integer of 1 or more, and f is an integer of 2 or more. ]

Examples of dimethylpolysiloxane blocked with a dimethylhydrogensiloxy group at both ends of the molecular chain include, for example, a compound represented by the following general formula [X], and further a part or all of the methyl group in the following general formula [X] is an ethyl group or propyl And a compound substituted with a group, a phenyl group, a trifluoropropyl group, and the like.
HSi (CH ₃ ) ₂ O — (— Si (CH ₃ ) ₂ —O—) _e —Si (CH ₃ ) ₂ H... [X]
[In the formula, e is an integer of 1 or more. ]

Examples of the dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane having both molecular chain ends include, for example, a compound represented by the following formula [XI], and further, part or all of the methyl group in the following formula [XI] is an ethyl group or a propyl group. , A phenyl group, a trifluoropropyl group, and the like.
_{_{HSi (CH 3) 2 O -}} (- SiH (CH 3) -O-) e -Si (CH 3) 2 H ··· [XI]
[In the formula, e is an integer of 1 or more. ]

Examples of the dimethylhydrogensiloxy group-blocked dimethyl siloxane / methyl hydrogen siloxane copolymer having both ends of the molecular chain include, for example, a compound represented by the following general formula [XII], and further a part of the methyl group in the following general formula [XII] Examples thereof include compounds in which all are substituted with an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group, or the like.
_{_{HSi (CH 3) 2 O -}} (- Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) h -Si (CH 3) 2 H ··· [XII]
[Wherein, e and h are each an integer of 1 or more. ]

Such a compound (B) can be produced by a known method, for example, octamethylcyclotetrasiloxane and / or tetramethylcyclotetrasiloxane and hexamethyldisiloxane or 1,3-dihydro which can be a terminal group. In the presence of a catalyst such as sulfuric acid, trifluoromethanesulfonic acid or methanesulfonic acid, a compound containing a triorganosilyl group or diorganohydrogensiloxy group, such as -1,1,3,3- tetramethyldisiloxane It can be easily obtained by equilibrating at a temperature of about −10 ° C. to + 40 ° C.

The compound (B) according to the present invention can be used alone or in combination of two or more.

[Compound (C) having a double bond in the molecule]
The compound (C) having a double bond in the molecule according to the present invention comprises an α-olefin (c1) having 6 to 3000 carbon atoms having a double bond at one end of the molecular chain [hereinafter simply referred to as an α-olefin ( may be referred to as c1). ] A diolefin (c2) having 6 to 3000 carbon atoms having double bonds at both ends of the molecular chain [hereinafter sometimes referred to simply as a diolefin (c2). It is preferable that any of the compounds is compatible with the copolymer (A) according to the present invention.

Compound (C) having double bond in molecule according to the present invention [Hereinafter, in the present invention, it may be simply referred to as compound (C). ] Is compatible with the copolymer (A) and imparts adhesiveness (adhesion) to the copolymer (A). In the present invention, by using a specific amount of the compound (C), water resistance (moisture resistance) resistance, heat resistance, polar solvent resistance, rubber elasticity, filling property can be improved, and crosslinking is possible even at room temperature. Liquid composition can be obtained. In the present invention, the term “compatible” means that it is transparent with no cloudiness or white turbidity when viewed.

When the screen printing copolymer composition of the present invention contains a compound (C) having a double bond in the molecule, it is usually 0.1 to 100 parts by weight of the copolymer (A). 100 parts by weight, preferably 0.1 to 75 parts by weight, more preferably 0.1 to 50 parts by weight, still more preferably 0.2 to 30 parts by weight, particularly preferably 0.2 to 20 parts by weight, and more particularly more preferably The amount is preferably 0.5 to 20 parts by weight, and is most preferably used in a ratio of 1.0 to 20 parts by weight, because it is particularly excellent in tackiness (adhesiveness).

Within the above range, a copolymer composition for screen printing having excellent flexibility and adhesiveness, water resistance (moisture resistance) and heat resistance can be obtained. On the other hand, if the amount of the compound (C) having a double bond in the molecule exceeds 100 parts by weight, it is not preferable because it is disadvantageous in terms of cost.

In the present invention, α-olefin (c1) is used as compound (C) having a double bond in the molecule for reasons such as compatibility with copolymer (A) and adhesion (adhesion). In this case, it is usually 0.1 to 50 parts by weight, preferably 0.2 to 30 parts by weight, more preferably 0.2 to 20 parts by weight with respect to 100 parts by weight of the copolymer (A). is there.

[Α-olefin (c1) having double bond at one end of molecular chain]
The α-olefin (c1) according to the present invention is compatible with the copolymer (C) and has 6 to 3000 carbon atoms, preferably 6 to 100 carbon atoms, more preferably 8 to 50 carbon atoms. More preferably, it has 8 to 30 carbon atoms. The α-olefin contains a vinyl or vinylidene type double bond at one end of the molecular chain. The α-olefin (c1) may be linear or branched, and is not limited to structural isomers such as trans isomers and cis isomers as long as the effects of the present invention are exhibited. Moreover, you may have a substituent which has a halogen, an oxygen atom, a nitrogen atom, etc. in the range which does not impair the effect of this invention.

The α-olefin (c1) according to the present invention can be polymerized by a known method and is not particularly limited to the production method. For example, JP-A-7-133234, JP-A-2003-261602, JP-A-2005-105286. Polymerization can be performed according to the publication.

Specific examples of the α-olefin (c1) according to the present invention include 1-hexene, 1-heptene, 4-methyl-1-hexene, 1-octene, 1-nonene, 1-decene, 2- Methyl-1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-icosene, 1-henicosene, 1-docosene, 1-tricosene, 1-tetracocene, 1-pentacocene, 1-hexacocene, 1-heptacocene, 1-octacocene, 1-nonacocene, 1-triacocene (1-triacontene), 1-tetracosene (1-tetracontain) ), 1-pentacontene, 1-hexene, etc., and linear α-olefins are preferred. 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-icocene are more preferable.

[Diolefin (c2) having double bonds at both ends of the molecular chain]
The diolefin (c2) according to the present invention is compatible with the copolymer (A) and has 6 to 3000 carbon atoms, preferably 6 to 100 carbon atoms, more preferably 8 to 50 carbon atoms, More preferably, it has 8 to 30 carbon atoms. The diolefin contains vinyl or vinylidene type double bonds at both ends of the molecular chain. Further, the diolefin (c2) may be linear or branched, and is not limited to structural isomers such as a trans isomer and a cis isomer as long as the effects of the present invention are exhibited. Moreover, you may have a substituent which has a halogen, an oxygen atom, a nitrogen atom, etc. in the range which does not impair the effect of this invention. In addition, both terminal means the terminal which exists in both of a principal chain in diolefin (c2).

The diolefin (c2) according to the present invention can be polymerized by a known method and is not particularly limited to the production method. For example, it can be polymerized according to Japanese Patent Application Laid-Open No. 9-87312 and International Publication No. WO2005 / 030681.

Specific examples of the diolefin (c2) according to the present invention include 1,5-hexadiene, 1,6-heptadiene, 3-methyl-1,5-hexadiene, 1,7-octadiene, and 3-methyl. -1,7-octadiene, 1,8-nonadiene, 3-methyl-1,8-nonadiene, 1,9-decadiene, 2-methyl-1-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1 , 12-tridecadiene, 1,13-tetradecadiene, 1,14-pentadecadiene, 1,15-hexadecadiene, 1,16-heptadecadiene, 1,17-octadecadiene, 1,18-nonadecadiene, , 19-eicosienene (1,19-icosodiene), 1,20-henicosediene, 1,21-docosediene, 1,22-trichosedie 1,3-tetracosediene, 1,24-pentacosediene, 1,25-hexacosediene, 1,26-heptacosediene, 1,27-octacosediene, 1,28-nonacosediene, 1,29-triaconthediene, 1,39-tetra Contediene, 1,49-pentacondiene, 1,99-hectadiene and the like can be mentioned, and linear diolefins are preferable, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1 , 8-nonadiene and 1,9-decadiene are more preferable.

[Terpene resin (D)]
In the present invention, the use of the terpene resin (D) is preferable because stronger adhesiveness can be obtained. In this case, although not particularly limited, the terpene resin is preferably contained in the composition in an amount of 1 to 300 parts by weight, more preferably 10 to 200 parts by weight with respect to 100 parts by weight of the copolymer (A). is there.

The terpene resin (D) is compatible with the copolymer (A), has 7 or more carbon atoms, more preferably 8 to 100 carbon atoms, and a number average molecular weight of 2000 or less, preferably 100 to 100. 1800. The number average molecular weight of the terpene resin (D) can be measured by a known gel permeation chromatography (GPC). For example, the chromatogram obtained by measuring using a known analytical instrument such as a liquid chromatograph. Can be obtained by analyzing using a calibration curve using a standard polystyrene sample.

In addition, the terpene resin contains a carbon-carbon double bond inside the molecular chain and / or a vinyl or vinylidene type double bond at one or more of one end and both ends. The double bond in the molecular chain may be a cycloalkene such as cyclohexene or a cycloolefin, and may be an aromatic compound as long as the effects of the present invention are exhibited. The terpene resin may be one in which a double bond contained in the molecular chain or at the terminal is saturated by hydrogenation. The terpene resin may contain a structural isomer such as a trans isomer or a cis isomer as long as the effects of the present invention are exhibited. Moreover, you may have a substituent which has a halogen, an oxygen atom, a nitrogen atom, etc. in the range which does not impair the effect of this invention. In addition, a both terminal means the terminal which exists in both of a principal chain in terpene resin (D).

Specific examples of the terpene resin (D) according to the present invention include, for example, α-pinene, β-pinene, dipentene, d-limonene, myrcene, alloocimene, ocimene, α-ferrandrene, α-terpinene, γ A resin containing a structure derived from a monoterpene such as terpinene, terpineolene, 1,8-cineole, 1,4-cineole, α-terpineol, β-terpineol, γ-terpineol, sabinene, paramentadienes, carenes, Examples include resins containing structures derived from sesquiterpenes such as longifolene, rosin, carotene, isoprene rubber, natural rubber, hydrogenated terpene resin, aromatic modified terpene resin, aromatic modified hydrogenated terpene resin, terpene phenol resin, etc. The Limonene is obtained by fractional distillation of orange oil, lemon oil, tangerine oil, camphor white oil and wood turpentine oil, and is represented by the chemical formula of C ₁₀ H ₁₆ , d-, l-, dl The isomer of-is present, but is not particularly limited. It can also be obtained from Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd., Yasuhara Chemical Co., Ltd., Arakawa Chemical Industries, Ltd.

Among these terpene resins (D), terpene resins preferably containing a structure derived from limonene, modified terpene resins, hydrogenated terpene resins, aromatic modified terpene resins, aromatic modified hydrogenated terpene resins, terpene phenol resins More preferably, it is an aromatic modified hydrogenated terpene resin.

In the present invention, as long as the effects of the present invention are exhibited, together with the terpene resin (D), rosins, rosin derivatives, petroleum resins and hydrogenated products thereof, DCPD resin, coumarone resin, coumarone indene resin, styrene Known resins that can impart tackiness, such as resin based resins, can be used.

These compounds can be used singly or in combination of two or more, or two or more α-olefin, diolefin and terpene resin can be used in combination, preferably alone or 2 It is to use in combination of more than species.

[Catalyst used for hydrosilylation reaction]
Catalyst used for hydrosilylation reaction contained in the copolymer composition for screen printing of the present invention as an optional component [hereinafter sometimes simply referred to as catalyst. ] Is an addition reaction catalyst and is not particularly limited as long as it promotes the addition reaction (alkene hydrosilylation reaction) between the alkenyl group in the copolymer (A) and the SiH group of the compound (B). For example, an addition reaction catalyst composed of a platinum group element such as a platinum-based catalyst, a palladium-based catalyst, or a rhodium-based catalyst (a group 8 metal catalyst such as a group 8 metal, group 8 metal complex, or group 8 metal compound in the periodic table) Can be mentioned. In the present invention, it is desirable to use a complex of a group 8 element metal of the periodic table and a compound containing a vinyl group and / or a carbonyl group. As the group 8 element metal of the periodic table, platinum is particularly preferable.

The platinum-based catalyst may be a known one that is usually used for addition-curing type curing, such as a finely powdered platinum metal catalyst described in US Pat. No. 2,970,150, US Pat. No. 2,823, No. 218, chloroplatinic acid catalyst, U.S. Pat. No. 3,159,601 and U.S. Pat. No. 159,662, complex compounds of platinum and hydrocarbons, U.S. Pat. Complex of chloroplatinic acid and olefin described in US Pat. No. 5,516,946, platinum and vinylsiloxane described in US Pat. No. 3,775,452 and US Pat. No. 3,814,780 And complex compounds. More specifically, examples include platinum alone (platinum black), chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, or a carrier such as alumina or silica on which a platinum carrier is supported.

As the compound containing a vinyl group, a vinyl group-containing organosiloxane is preferable. Specific examples of complexes of these with platinum include platinum-divinyltetramethyldisiloxane complex, platinum-divinyltetraethyldisiloxane complex, platinum-divinyltetrapropyldisiloxane complex, platinum-divinyltetrabutyldisiloxane complex, platinum -Divinyltetraphenyldisiloxane complex.

As the compound containing a carbonyl group, carbonyl, octanal and the like are preferable. Specific examples of the complex of these with platinum include a platinum-carbonyl complex, a platinum-octanal complex, a platinum-carbonylbutyl cyclic siloxane complex, and a platinum-carbonylphenyl cyclic siloxane complex.

Among vinyl group-containing organosiloxanes, vinyl group-containing cyclic organosiloxanes are preferred. Examples of the complex of these with platinum include a platinum-vinylmethyl cyclic siloxane complex, a platinum-vinylethyl cyclic siloxane complex, and a platinum-vinylpropyl cyclic siloxane complex. The vinyl group-containing organosiloxane itself may be a ligand for a metal, but may be used as a solvent for coordinating other ligands. A complex in which a vinyl group-containing organosiloxane is used as a solvent and the above-mentioned compound containing a carbonyl group is a ligand is particularly preferred as a catalyst used in the hydrosilylation reaction of the present invention.

Specific examples of such complexes include a platinum-carbonyl complex vinylmethyl cyclic siloxane solution, a platinum-carbonyl complex vinylethyl cyclic siloxane solution, a platinum-carbonyl complex vinylpropyl cyclic siloxane solution, and a platinum-carbonyl complex divinyl. Tetramethyldisiloxane solution, platinum-carbonyl complex divinyltetraethyldisiloxane solution, platinum-carbonyl complex divinyltetrapropyldisiloxane solution, platinum-carbonyl complex divinyltetrabutyldisiloxane solution, platinum-carbonyl complex divinyltetraphenyldi A siloxane solution is mentioned.

The catalyst comprising these complexes may further contain components other than the compound containing a vinyl group and / or a carbonyl group. For example, a solvent other than a compound containing a vinyl group and / or a carbonyl group may be contained. Examples of these solvents include various alcohols and xylene, but are not limited thereto.

Specific examples of the alcohol include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol. , Aliphatic saturated alcohols such as capryl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and eicosyl alcohol; fats such as allyl alcohol and crotyl alcohol Unsaturated alcohols; cycloaliphatic alcohols such as cyclopentanol and cyclohexanol; benzyl alcohol, cinnamyl alcohol Aromatic alcohols such as call; and heterocyclic alcohols such as furfuryl alcohol.

An example of using alcohol as a solvent is a platinum-octanal / octanol complex. By including these solvents, there are advantages such as easy handling of the catalyst and easy mixing with the rubber composition. Among the various catalysts mentioned above, a platinum-carbonyl complex vinylmethyl cyclic siloxane solution (in particular, a complex represented by the following chemical formula 1 is preferred), a platinum-vinylmethyl cyclic siloxane complex (among others, a complex represented by the chemical formula 2 is preferred). ), A platinum-divinyltetramethyldisiloxane complex (in particular, a complex represented by the chemical formula 3), a platinum-octanal / octanol complex, and the like are practically preferred, and among them, a platinum-carbonylvinylmethyl cyclic siloxane complex is particularly preferred.
Chemical formula 1: Pt ⁰ · CO · (CH ₂ ═CH (Me) SiO) ₄
Chemical formula 2: Pt ⁰ · (CH ₂ ═CH (Me) SiO) ₄
Chemical formula 3: Pt ⁰ -1.5 [(CH ₂ ═CH (Me) ₂ Si) ₂ O]

The palladium-based catalyst is composed of palladium, a palladium compound, chloropalladic acid, and the rhodium-based catalyst is composed of rhodium, a rhodium compound, rhodium chloride, and the like.

Examples of catalysts other than the above include Lewis acids and cobalt carbonyl.

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

The proportion of group 8 element metal (preferably platinum) contained in these catalysts is usually 0.1 to 10% by weight, preferably 1 to 5% by weight, more preferably 2 to 4% by weight.

When the screen printing copolymer composition according to the present invention contains a catalyst, it is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight per 100 parts by weight of the copolymer (A). Part by weight, more preferably 0.1 to 3 parts by weight is used.

When the catalyst used for the hydrosilylation reaction is used within the above range, a copolymer composition for screen printing excellent in processability and curing speed can be formed. If it is used at a ratio exceeding 10 parts by weight, it is not preferable because it is disadvantageous in terms of cost.

[Antifoaming agent (X)]
As the antifoaming agent (X) according to the present invention, those used for non-aqueous systems can be used, and representative examples include silicones such as dimethylpolysiloxane, modified butadienes, polyethers, acrylics, and vinyls. And mixtures thereof. These can be obtained from Shin-Etsu Silicone, Toray Dow Corning, Kao, Sanyo Kasei, Enomoto Kasei, Nisshin Chemical Research Laboratories, etc.

When the antifoaming agent is included as the screen printing copolymer composition, 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight, with respect to 100 parts by weight of the screen printing copolymer composition, More preferably, it is in the range of 0.2 to 1.0 part by weight.

(Reaction inhibitor)
In this invention, you may use a well-known reaction inhibitor as an arbitrary component in the range which does not impair the objective of this invention.

The reaction inhibitor is not particularly limited. For example, benzotriazole, ethynyl group-containing alcohol (for example, 1-ethynyl-2-ethyl-1-hexanol, ethynylcyclohexanol), acrylonitrile, amide compound (for example, N, N -Dialylacetamide, N, N-diallylbenzamide, N, N, N ', N'-tetraallyl-o-phthalic acid diamide, N, N, N', N'-tetraallyl-m-phthalic acid diamide, N, N , N ', N'-tetraallyl-p-phthalic acid diamide, etc.), sulfur, phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, tetramethyltetravinylcyclotetrasiloxane, hydroperoxide, etc. An organic peroxide etc. are mentioned.

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

The screen printing copolymer composition is not particularly limited when it contains a reaction inhibitor, but is usually 0 to 50 parts by weight, preferably 0.0001 to 50 parts per 100 parts by weight of the copolymer (A). Parts by weight, more preferably 0.0001-30 parts by weight, still more preferably 0.0001-20 parts by weight, particularly preferably 0.0001-10 parts by weight, most preferably 0.0001-5 parts by weight. It is done. When used in a proportion of 50 parts by weight or less, a copolymer composition for screen printing having a moderate crosslinking rate and excellent screen printing properties can be obtained. If it exceeds 50 parts by weight, it may be disadvantageous in terms of cost.

〔Silane coupling agent〕
In this invention, you may use a well-known silane coupling agent as an arbitrary component in the range which does not impair the objective of this invention.

A silane coupling agent is usually used for the purpose of further improving self-adhesion. Examples of the silane coupling agent include an acrylic (methacrylic) functional silane coupling agent, an epoxy functional silane coupling agent, and an amino (imino) functional silane coupling agent.

Specific examples of acrylic (methacrylic) functional silane coupling agents include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltriethoxy. Examples include silane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.

Specific examples of the epoxy functional silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and the like.

Specific examples of amino (imino) functional silane coupling agents include H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , (C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si An amino group such as (OC ₂ H ₅ ) ₃ and / or an imino group-containing alkoxysilane; the amino group and / or imino group-containing alkoxysilane;

A reaction product with an epoxy silane compound such as: an aminosilane and / or imino group-containing alkoxysilane, and CH ₂ ═C (CH ₃ ) COOCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CH ₂ ═ Examples thereof include a reaction product with a methacryloxysilane compound such as C (CH ₃ ) COOCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₂ OCH ₃ ) ₃ .

When the silane coupling agent is included as the screen printing copolymer composition, it is not particularly limited, but is preferably based on 100 parts by weight of the total amount of the copolymer (A) and the compound (B). It is used in a proportion of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight.

[Plasticizer]
In the present invention, various known plasticizers may be used as optional components as long as the object of the present invention is not impaired.

Specifically, for example, paraffinic process oil, naphthenic process oil, aromatic process oil, ethylene and α-olefin co-oligomer, paraffin wax, liquid paraffin, white oil, petrolatum, lubricating oil, petroleum asphalt, petroleum jelly Petroleum softeners such as coal tar and coal tar pitch; coal tar softeners such as castor oil, linseed oil, rapeseed oil and coconut oil; tall oils; petroleum resins, atactic polypropylene, Synthetic polymer materials such as coumarone indene resin; phthalic acid derivatives, isophthalic acid derivatives, tetrahydrophthalic acid derivatives, adipic acid derivatives, azelaic acid derivatives, sebacic acid derivatives, dodecane-2-succinic acid derivatives, maleic acid derivatives, fumaric acid derivatives , Trimellitic acid derivatives, pyromellitic Tolic acid derivatives, citric acid derivatives, itaconic acid derivatives, oleic acid derivatives, ricinoleic acid derivatives, stearic acid derivatives, phosphoric acid derivatives, sulfonic acid derivatives, glycerin derivatives, glutaric acid derivatives, epoxy derivatives, glycol derivatives, paraffin derivatives, silicone oil And so on.

Among them, ethylene and α-olefin co-oligomers, process oils, and paraffin derivatives that do not inhibit the silylation reaction are preferably used, and paraffinic process oils and ethylene and α-olefin co-oligomers are particularly preferably used. . In particular, a plasticizer that does not inhibit the hydrosilylation reaction is preferable. Specifically, a plasticizer in which the content of a sulfur compound, a nitrogen compound, an amine compound, and a phosphorus compound is 100 ppm or less is preferable.

When the copolymer for screen printing contains a plasticizer, it is not particularly limited, but is usually 0 to 1000 parts by weight, preferably 1 to 1000 parts by weight, with respect to 100 parts by weight of the copolymer (A). More preferably 5 to 800 parts by weight, still more preferably 10 to 700 parts by weight, particularly preferably 20 to 500 parts by weight, and most preferably 30 to 300 parts by weight. When used in the above proportion, the fluidity is improved and the moldability is improved. Moreover, when it uses in the ratio exceeding 1000 weight part, there exists a possibility that an intensity | strength characteristic may deteriorate, it is unpreferable.

[Stabilizer]
Examples of the stabilizer used as necessary in the present invention include a heat resistance stabilizer, a weather resistance stabilizer, a hindered amine stabilizer, and the like. Examples of the heat-resistant stabilizer used as necessary in the present invention include a phenol-based stabilizer, a phosphorus-based stabilizer, and a sulfur-based stabilizer.

As the phenol-based stabilizer, a phenol-based stabilizer conventionally used as a stabilizer is used without any particular limitation. Specific examples of phenolic stabilizers include β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearyl ester, tetrakis [methylene-3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-t-hydroxybenzyl) benzene, dl-α-tocopherol, tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, tris [(3,5-di -T-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl) -4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-spiro [5.5] undecane is preferred.

Commercially available products may be used as the phenol-based stabilizer, such as Irganox 1010 (Irganox 1010, Ciba Geigy, Trademark), Irganox 1035 (Irganox 1035, Ciba Geigy, Trademark), Irganox 1076 (Irganox 1076, Ciba Geigy, Trademark), Irganox, and the like. 1135 (Irganox 1135, Ciba-Geigy, Trademark), Irganox 1330 (Irganox 1330, Ciba-Geigy, Trademark), Irganox 3114 (Irganox 3114, Ciba-Geigy, Trademark), Irganox 3125 (Irganox 3125, Ciba-Geigy H, Trademark, B) ), Trademark), Cyanox 1790 (Cyanox 1790, Cyanamid Co., Ltd.), Smizer GA-80 (SumilizerGA-80, Sumitomo Chemical Co., trademark), vitamin E (Eisai Co.) and the like. These phenolic stabilizers can be used alone or in combination.

The compounding amount of the phenol-based stabilizer is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the copolymer (A). Is desirable. When the content of the phenol-based stabilizer is in the above range with respect to 100 parts by weight of the copolymer (A), the effect of improving the stability such as heat resistance and aging resistance is high, and the stabilizer Thus, the costs of the copolymer (A), such as the tensile strength after the heat aging test, are not lowered.

As the phosphorus stabilizer, a phosphorus stabilizer conventionally used as a stabilizer is used without any particular limitation. Commercially available products may be used as the phosphorus stabilizer, such as Irgafos 168 (Irgafos 168, Ciba Geigy, Trademark), Irgafos 12 (Irgafos 12, Ciba Geigy, Trademark), Irgafos 38 (Irgafos 38, Ciba Geigy, Trademark), Mark 329K (Mark 329K, Asahi Denka Co., Ltd., trademark), Mark PEP36 (Mark PEP36, Asahi Denka Co., Ltd., trademark), Mark PEP-8 (Mark PEP-8, Asahi Denka Co., Ltd., trademark), Sandtab P- EPQ (Clariant, trademark), Weston 618 (Weston 618, GE, trademark), Weston 619G (Weston 619G, GE, trademark), Weston-624 (Weston-624, GE, trademark), and the like. These phosphorus stabilizers can be used alone or in combination.

The compounding amount of the phosphorus stabilizer is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the copolymer (A). Is desirable. When the content of the phosphorus stabilizer is within the above range with respect to 100 parts by weight of the copolymer (A), the effect of improving stability such as heat resistance and aging resistance is high and stable. The cost of the agent is kept at a low price, and the properties of the copolymer (A), such as the tensile strength after the heat aging test, are not lowered.

As the sulfur stabilizer, a sulfur stabilizer conventionally used as a stabilizer is used without any particular limitation. Specific examples of the sulfur stabilizers include dialkylthiodipropionates such as dilauryl-, dimyristyl-, and distearyl- and polyhydric alcohols such as alkylthiopropionic acids such as butyl-, octyl-, lauryl-, and stearyl- Examples thereof include esters of glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (for example, pentaerythritol tetralauryl thiopropionate).

Commercially available products may be used as the sulfur stabilizer, such as DSTP (Yoshitomi) (Yoshitomi Pharmaceutical Co., Ltd., Trademark), DLTP (Yoshitomi) (Yoshitomi Pharmaceutical Co., Ltd., Trademark), DLTOIB (Yoshitomi Pharmaceutical). (Co., Ltd., Trademark), DMTP (Yoshitomi) (Yoshitomi Pharmaceutical Co., Ltd., Trademark), Seenox 412S (Shiraishi Calcium Co., Ltd., Trademark), Cyanox 1212 (Cyanamide, Trademark) and the like. These sulfur stabilizers can be used alone or in combination.

The compounding amount of the sulfur stabilizer is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the copolymer (A). Is desirable. When the content of the sulfur stabilizer is in the above range with respect to 100 parts by weight of the copolymer (A), the effect of improving the stability such as heat resistance and aging resistance is high, and the stabilizer. Thus, the costs of the copolymer (A), such as the tensile strength after the heat aging test, are not lowered.

The weather stabilizer used as necessary in the present invention is roughly classified into an ultraviolet absorber and a light stabilizer.

Specific examples of UV absorbers include salicylic acid UV absorbers, benzophenone UV absorbers, benzotriazole absorbers, and cyanoacrylate UV absorbers.

The ultraviolet absorber is in a proportion of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 3 parts by weight, relative to 100 parts by weight of the copolymer (A). Used. As the light stabilizer, a conventionally known light stabilizer can be used, and among them, a hindered amine light stabilizer (HALS; Hindered Amine Light Stabilizers) is preferably used. Specifically, the following compounds are used as the hindered amine light stabilizer.

Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate , Poly {[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2-4-diyl] [(2,2,6,6-tetramethyl-4- Piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 , 4-butanetetracarboxylate, 1,1 ′-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), mixed {2,2,6,6-tetramethyl -4-piperidyl / β, β, β , Β'-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro (5.5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, poly {[6 -N-morpholyl-1,3,5-triazine-2--4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6- Tetramethyl-4-piperidyl) imino]} and a condensate of N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane.

These hindered amine light stabilizers may be used alone or in combination.

The hindered amine light stabilizer is added in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 3 parts by weight based on 100 parts by weight of the copolymer (A). It is desirable to use parts by weight. When the content of the hindered amine light stabilizer is within the above range with respect to 100 parts by weight of the copolymer (A), the effect of improving stability such as heat resistance and aging resistance is high, and light The cost of the stabilizer can be kept at a low price, and the properties of the copolymer (A) such as the tensile strength after the weather resistance test are not lowered.
[Curing shrinkage]
The curing shrinkage of the screen printing copolymer composition of the present invention is usually 5% or less, preferably 4.0% or less, and more preferably 3.0% or less.

[Refractive index]
The refractive index of the screen-printing copolymer composition of the present invention is usually in the range of 1.45 to 1.55, preferably 1.47 to 1.55. When the refractive index is in the above range, the visibility is excellent.

(Light transmittance)
The light transmittance in the visible light region of the copolymer composition for screen printing of the present invention is 90% or more, preferably 93% or more, more preferably 95% or more when the thickness of the layer after curing is 100 μm. It is prepared as follows.

The cured product of the copolymer composition present in the gap between the image display part and the protective part has a light transmittance of 90% or more and a refractive index (nD) of 1.45 to 1.55, preferably 1.47 to 1. .55 makes it possible to improve the visibility by increasing the brightness and contrast of the image light from the image display unit.

Here, the distortion of the image display unit and the protection unit means that the influence of stress during the effective shrinkage of the resin can be minimized with respect to the image display unit and the protection unit. Say that there is almost no distortion. For example, in general, when a condensation curable resin is used as an adhesive, if the resin is cured and bonded after bonding, problems such as volume shrinkage and distortion of the bonded surface may occur. However, since the resin composition of the present invention has a small volume change at the time of curing, distortion due to resin curing hardly occurs between the image display part filled with the resin and the protective part.

[Laminate]
The laminate of the present invention is a laminate obtained by screen printing the copolymer composition for screen printing of the present invention on a substrate having at least one plane.

The substrate having at least one plane is not particularly limited as long as it has a shape having at least a part of a plane, and substrates having various known shapes can be used. Specifically, for example, in addition to a planar substrate such as a sheet or a film, a cylinder, a container, a bottle, a polarizing plate or the like partially provided with a plane can be exemplified. The material may be glass or resin, but is not limited thereto.

In the laminate of the present invention, the thickness of the layer obtained after the screen-printing copolymer composition of the present invention is screen-printed and cured can usually be 25 to 250 μm.

[Screen printing method]
As a method for screen-printing the screen-printing copolymer composition of the present invention, a method for applying the screen-printing copolymer composition of the present invention to the surface of the touch panel substrate will be described. The board | substrate to print is not specifically limited, For example, a plastic film, glass, a polarizing plate etc. are mentioned. First, the surface of the substrate is covered with a mask having openings of a required pattern, and the composition of the present invention is put into the squeegee portion. Next, the composition is filled in the opening of the masking member by moving the squeegee to move the mask while pressurizing the composition (filling step). Next, the mask is removed. Thus, a pattern of the composition can be formed on the surface of the substrate.

The pattern of the composition thus formed is then cured. Curing is in the range of room temperature to 100 ° C., preferably room temperature to 60 ° C., and the curing time is 1 minute to 48 hours, preferably 5 minutes to 1 day, more preferably 5 minutes to 1 hour. However, it is also possible to irradiate with ultraviolet rays by using a UV light irradiation device together.

[Touch panel]
The touch panel of the present invention is not particularly limited, and may be any type such as a capacitance type, a resistance film type, an optical type, and an ultrasonic type.

The following examples are given as examples of the configuration of a typical touch panel used in the present invention, but are not limited thereto.

In the case of a capacitive touch panel in which the present invention is used, for example, a transparent electrode such as ITO is formed on a glass substrate, and the transparent electrode is further opposed to the insulating layer. The transparent electrode may be formed on a glass substrate or may be formed on a resin film such as PET.

The copolymer composition for screen printing of the present invention is mainly used for bonding or filling between the touch panel and the protective part, and between the touch panel and the display device. In addition, it may be used for bonding or filling applications such as bonding between electrodes.

[Manufacturing method of touch panel]
The touch panel of the present invention can be manufactured by a known method. You may use the composition of this invention also about the bonding of the glass substrate which formed the transparent electrode which comprises a touch panel, and an ITO film.

[Method of manufacturing display device having touch panel]
The touch panel of the present invention is combined with various display devices to constitute a display device. Examples of the display device include a liquid crystal display device, an inorganic EL device, an organic EL device, a cathode ray tube (CRT), a plasma display (PDP), and a field emission display (FED). Usually, a display device having such a touch panel is composed of display devices such as a cover glass, a touch panel, and a liquid crystal device as viewed from the input surface. Between these elements and panels, the composition of the present invention can be screen-printed and bonded.

The bonding process is not particularly limited. For example, in manufacturing a display device including a cover glass, a touch panel, and a liquid crystal display device, first, the composition of the present invention is screen-printed on the touch panel, and the cover glass is pressure-bonded. And the composition is heat-cured. You may perform a heat-hardening process before bonding. Furthermore, a display device can be obtained by screen-printing the composition on the opposite surface of the touch panel, pasting it with a liquid crystal display device, and curing by heating.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the present invention, each physical property was evaluated as follows.

[Various measurement conditions]
[1] Viscosity (Pa · s)
Using an E-type viscometer (TVW-25) manufactured by Toki Sangyo Co., Ltd., cone plate (angle: 1 degree × R24 mm, or 3 degrees × R14 mm), rotation speed: 0.1 to 100 rpm, sample amount: The viscosity was measured at 25 ° C. under the conditions of 0.6 to 1.0 g and the value showing the same value for 30 seconds or more was taken as the viscosity.

[2] Refractive index Using the adjusted copolymer composition for screen printing, a 120 × 120 × 2 mm sheet was prepared, and a part thereof was used to prepare an Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.). Measurement wavelength: D line (589 nm), measurement was performed at a test temperature of 23 ° C.

[3] Light transmittance The transmittance of a sample piece obtained by bonding a screen-printing copolymer composition to two pieces of glass at a pressure of 100 μm, and a sample piece without anything sandwiched between them are spectrophotometers (Hitachi High-Tech Fielding Co., Ltd.). : U-3310), and the transmittance at a wavelength of 500 nm was taken as the measured value.

[Example 1]
[Production of ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-1)]
Using a stainless steel polymerization vessel (stirring rotation speed = 250 rpm) with a substantial internal volume of 100 liters equipped with stirring blades, ethylene, propylene, and 5-vinyl-2-norbornene (hereinafter abbreviated as VNB) are used. Original copolymerization was performed. From the side of the polymerization vessel to the liquid phase, 42 liters of hexane per hour, 2.1 kg of ethylene, 1.9 kg of propylene, 400 g of VNB, 515 liters of hydrogen, 280 mmol of VOCl ₃ as a catalyst, Al (Et) ₂ Cl was continuously fed at a rate of 840 mmol and Al (Et) _1.5 Cl _1.5 at a rate of 840 mmol. The polymerization temperature was 45 ° C., and the polymerization pressure was 7.5 kgf / cm ² (0.75 MPa).

When the copolymerization reaction was carried out under the conditions described above, an ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-1) was obtained in a uniform solution state.

Thereafter, a small amount of methanol is added to the polymerization solution continuously extracted from the lower part of the polymerization vessel to stop the polymerization reaction, and the polymer is separated from the solvent by a steam stripping treatment, followed by vacuum drying at 55 ° C. for 48 hours. Went.

The ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-1) thus obtained had an ethylene unit [i] / α-olefin unit [ii] molar ratio ([i] / [ii]). Is 61.5 mol% / 37.0 mol%, iodine value is 10.0 g / 100 g, intrinsic viscosity (in 135 ° C. decalin solution) is 0.27 (dl / g), Mn is 3160, and viscosity is 830 Pa · s. Met.

[Production of copolymer composition for screen printing]
Copolymer (A-1) obtained by the above production method: 100 parts by weight of mineral oil [trade name PW-32 manufactured by Idemitsu Kosan Co., Ltd.]: 300 parts by weight of the following formula (XIII) Hydrosilyl group-containing compound (B-1) [manufactured by Shin-Etsu Chemical Co., Ltd., trade name X93-916]: 4.3 parts by weight, reaction inhibitor of the following formula (XIV) [manufactured by Shin-Etsu Chemical Co., Ltd. No. X93-1036]: 0.1 parts by weight, and an antifoaming agent (trade name Disparon LAP-10 manufactured by Enomoto Kasei Co., Ltd.): 0.6 parts by weight were mixed. Thereafter, the mixture was stirred for 300 seconds or more at room temperature using a stirrer (manufactured by THINKY Co., Ltd., product name: Aritori Netaro ARE-250). After cooling, 0.4 parts by weight of a platinum catalyst (3% Pt-CTS-CTS solution manufactured by N.E. Chemcat Co., Ltd.) was added, and the mixture was further stirred for 10 seconds or more and taken out to obtain a copolymer for screen printing. A composition was obtained.

The composition viscosity (25 ° C.) immediately after blending of the obtained composition was 1.40 Pa · s. The refractive index of the molded product after crosslinking of the obtained composition was 1.474. The obtained cross-linked product was applied to a thickness of 100 μm using a 50-mesh screen printer and bonded to the substrate. Immediately confirmed that the resin had spread over the entire surface of the substrate, heated at 60 ° C. for 30 minutes for adhesion. It was.

The results are shown in Table 1.

[Comparative Example 1]
Using the resin composition prepared in Example 1, using a dispenser (Nippon Labor-saving Research Laboratories, Inc .: ID-200N), adjusting the coating amount to a thickness of 100 μm, coating on the substrate, and bonding the substrates together Implemented and evaluated processability. After 30 minutes, it was confirmed that the resin had spread over the entire surface of the substrate, and heated at 60 ° C. for 30 minutes for adhesion. The results are shown in Table 1.

[Example 2]
Instead of the composition used in Example 1, the mineral oil [trade name PW-32 manufactured by Idemitsu Kosan Co., Ltd.] is used with respect to 100 parts by weight of the copolymer (A-1) obtained in Example 1. : 250 parts by weight, hydrosilyl group-containing compound (B-1) of the above formula (XIII) [trade name X93-916, manufactured by Shin-Etsu Chemical Co., Ltd.]: 6.45 parts by weight, reaction inhibition of the above formula (XIV) Agent [trade name X93-1036 manufactured by Shin-Etsu Chemical Co., Ltd.]: 0.1 parts by weight, 1-octadecene [trade name Linearlen C-18 manufactured by Idemitsu Kosan Co., Ltd.]: 5.24 parts by weight, aromatic 50 parts by weight of a modified hydrogenated terpene resin [trade name Clearon M105 manufactured by Yashara Chemical Co., Ltd.] and 1.0 part by weight of an antifoaming agent [trade name Disparon LAP-10 manufactured by Enomoto Kasei Co., Ltd.] were mixed. Thereafter, the mixture was stirred for 300 seconds or more at room temperature using a stirrer (product name: Aritori Nertaro ARE-250, manufactured by THINKY). After cooling, 0.4 parts by weight of platinum-based catalyst (3% Pt-CTS-CTS solution manufactured by N.E. Chemcat Co., Ltd.) was added, and the mixture was stirred for 10 seconds or more and taken out to obtain a copolymer composition for screen printing. I got a thing.

The composition viscosity (25 ° C.) immediately after blending of the obtained composition was 2.7 Pa · s. The refractive index of the molded product after crosslinking of the obtained composition was 1.484. The obtained cross-linked product was applied to a thickness of 100 μm using a 50-mesh screen printing apparatus and bonded to the substrate. Immediately after confirming that the composition had spread over the entire surface of the substrate, heating was performed at 60 ° C. for 30 minutes. Glued.

The results are shown in Table 1.

Example 3
Instead of the composition used in Example 1, the mineral oil [trade name PW-32 manufactured by Idemitsu Kosan Co., Ltd.] is used with respect to 100 parts by weight of the copolymer (A-1) obtained in Example 1. : 300 parts by weight, hydrosilyl group-containing compound (B-1) of the above formula (XIII) [trade name X93-916, manufactured by Shin-Etsu Chemical Co., Ltd.]: 6.45 parts by weight, reaction inhibition of the above formula (XIV) Agent [trade name X93-1036 manufactured by Shin-Etsu Chemical Co., Ltd.]: 0.1 parts by weight, 1-octadecene [trade name Linearlen C-12 manufactured by Idemitsu Kosan Co., Ltd.]: 3.06 parts by weight, hydrogenated Styrenic resin [trade name FTR8100 manufactured by Mitsui Chemicals, Inc.]: 50 parts by weight, and antifoaming agent [trade name Disparon LAP-10, manufactured by Enomoto Kasei Co., Ltd.]: 0.6 parts by weight were mixed. Thereafter, the mixture was stirred for 300 seconds or more at room temperature using a stirrer (product name: Aritori Nertaro ARE-250, manufactured by THINKY). After cooling, 0.4 parts by weight of platinum-based catalyst (3% Pt-CTS-CTS solution manufactured by N.E. Chemcat Co., Ltd.) was added, and the mixture was stirred for 10 seconds or more and taken out to obtain a copolymer composition for screen printing. I got a thing.

The composition viscosity (25 ° C.) immediately after blending of the obtained composition was 1.60 Pa · s. The refractive index of the molded product after crosslinking of the obtained composition was 1.484. The obtained cross-linked product was applied to a thickness of 100 μm using a 50-mesh screen printer and bonded to the substrate. Immediately confirmed that the resin had spread over the entire surface of the substrate, heated at 60 ° C. for 30 minutes for adhesion. It was. The results are shown in Table 1.

Example 4
The same operation as in Example 1 was carried out except that an antifoaming agent (trade name Disparon LAP-10 manufactured by Enomoto Kasei Co., Ltd.) was not added. Foaming was observed when the screen substrate was released after coating, and it took 30 minutes or more until the foam disappeared, and the bonding processability deteriorated.

Example 5
[Production of ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-2)]
Using a stainless steel polymerization vessel (stirring rotation speed = 250 rpm) with a substantial internal volume of 100 liters equipped with stirring blades, three of ethylene, propylene and 5-vinyl-2-norbornene (hereinafter abbreviated as VNB) are continuously used. Original copolymerization was performed. From the side of the polymerization vessel to the liquid phase, 60 liters of hexane per hour, 1.3 kg of ethylene, 2.5 kg of propylene, 130 g of VNB, 30 liters of hydrogen, 23 VO (OEt) Cl ₂ as a catalyst Mmol, Al (Et) _1.5 Cl _1.5 was fed continuously at a rate of 161 mmol. A copolymerization reaction was carried out under the conditions described above and in Table 1 to obtain an ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-2) in a homogeneous solution state. Thereafter, a small amount of methanol is added to the polymerization solution continuously withdrawn from the lower part of the polymerization vessel to stop the polymerization reaction, and the polymer is separated from the solvent by a steam stripping treatment, followed by vacuum drying at 55 ° C. for 48 hours. Was done.

The ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-2) thus obtained has an ethylene unit [i] / α-olefin unit [ii] molar ratio ([i] / [ii]). Was 63.5 mol% / 33.0 mol%, iodine value was 23.5 g / 100 g, intrinsic viscosity (in 135 ° C. decalin solution) was 0.08 dl / g, Mn was 920, and viscosity was 10 Pa · s. .

[Production of copolymer composition for screen printing]
Copolymer (A-2) obtained by the above method: 100 parts by weight of the hydrosilyl group-containing compound (B-1) of the above formula (XIII) (trade name X93- manufactured by Shin-Etsu Chemical Co., Ltd.) 916): 10.1 parts by weight, reaction inhibitor of the above formula (XIV) (trade name X93-1036 manufactured by Shin-Etsu Chemical Co., Ltd.): 0.4 parts by weight, antifoaming agent (Enomoto Kasei Co., Ltd.) Product name Disparon LAP-10): 0.6 parts by weight were mixed. Thereafter, the mixture was stirred for 300 seconds or more at room temperature using a stirrer (product name: Aritori Netaro ARE-250, manufactured by THINKY). After cooling, 0.15 parts by weight of a platinum-based catalyst (3% Pt-CTS-CTS solution manufactured by N.E. Chemcat Co., Ltd.) is added, and after stirring for 10 seconds or more, the copolymer composition for screen printing is taken out. Got.

The composition viscosity (25 ° C.) immediately after blending of the obtained composition was 4.2 Pa · s. The refractive index of the molded product after crosslinking of the obtained composition was 1.484. The obtained cross-linked product was applied to a thickness of 100 μm by a 50-mesh screen printing apparatus and bonded to the substrate. After the resin had spread over the entire surface of the substrate, it was heated at 60 ° C. for 30 minutes to be bonded. The obtained crosslinked product was evaluated. The results are shown in Table 2.

[Examples 6 to 10]
Evaluation was carried out in the same manner as in Example 5 except that the raw materials, blending amount and coating method were changed according to Table 2. The results are shown in Table 2.

According to the present invention, when a substrate, a film, or the like is bonded to a touch panel or a display panel, it can be applied by screen printing, imparts sufficient adhesiveness, and is bonded without containing bubbles. An adhesive composition can be provided.

Claims

at least,
(A) a structural unit [i] satisfying the following requirements (a) to (c) and derived from ethylene, a structural unit [ii] derived from an α-olefin having 3 to 20 carbon atoms, An ethylene / α-olefin / nonconjugated polyene random copolymer (A) containing a structural unit [iii] derived from at least one nonconjugated polyene selected from the formulas [I] and [II] Copolymer composition for screen printing.
(A) The molar ratio of ethylene unit [i] / α-olefin unit [ii] ([i] / [ii]) is 35/65 to 95/5,
(B) the iodine value is in the range of 0.5-50,
(C) the intrinsic viscosity [η] measured in a decalin solution at 135 ° C. is in the range of 0.01 to 5.0 (dl / g);

(In the formula [I], n is an integer of 0 to 10, R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. is there).

(In the formula [II], R 3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).
The copolymer composition for screen printing according to claim 1, wherein the ethylene / α-olefin / non-conjugated polyene random copolymer (A) has a number average molecular weight (Mn) of 500 to 5,000.
The copolymer composition for screen printing according to claim 1 or 2, comprising a platinum-based catalyst.
The copolymer composition for screen printing according to any one of claims 1 to 3, further comprising an antifoaming agent (X).
The copolymer composition for screen printing according to any one of claims 1 to 4, wherein the copolymer composition has a viscosity of 0.1 to 100 Pa · s at 25 ° C.
The screen-printing copolymer composition according to any one of claims 1 to 5, wherein the screen-printing copolymer composition is an adhesive for a touch panel.
The screen-printing copolymer composition according to any one of claims 1 to 6, comprising a compound (C) having a double bond in the molecule.
A laminate obtained by screen-printing the copolymer composition according to any one of claims 1 to 7 on a substrate having at least one plane.
The laminate according to claim 8, which is obtained by crosslinking a screen-printed copolymer composition.
A method of screen printing the copolymer composition according to any one of claims 1 to 7 on a substrate.
A method for producing a touch panel, comprising screen-printing the screen-printing copolymer composition according to any one of claims 5 to 7 on a substrate of a display unit.
The method for producing a touch panel according to claim 11, wherein the screen-printing copolymer composition is crosslinked after screen printing.
The method for manufacturing a touch panel according to claim 11 or 12, wherein a solvent drying step is not included.
The touch panel obtained by the production method according to any one of claims 11 to 13, wherein the thickness of the screen printing copolymer composition is in the range of 25 to 250 µm.