JP2003261851A - Urethane resin type contact adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solventless urethane resin type contact adhesive shortened in the time up to the development of tackiness, developing high adhesive strength immediately after tacking, having a long tacking range and extended in laminatable time. <P>SOLUTION: This urethane resin type contact adhesive contains a urethane resin, which is a polyoxyalkylene polymer containing at least polyoxyethylene in its main chain and having an -RN-CO-NH- bond (wherein, R is a specific substituent) and a hydrolyzable silicon group in its molecule, and a tackifier resin as components. If a vinyl polymer is further combined with this adhesive, a tacking range or a laminatable time are further extended. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a urethane resin-based contact adhesive, and more specifically, the adhesive is applied to both sides or one side of an adherend to be adhered, and open time is taken to develop tack. The present invention relates to a urethane resin-based contact adhesive suitable for contact adhesion to be bonded later.

[0002]

2. Description of the Related Art A contact bonding method in which an adhesive agent is applied to both sides or one side of an adherend and is bonded after a predetermined open time elapses, exhibits excellent clamping strength immediately after bonding and does not require temporary pressing. . In addition, this contact bonding method is particularly effective in bonding non-porous materials together using a one-component adhesive. As a one-component adhesive used for such contact adhesion, a solvent-type rubber adhesive has long been known. However, this solvent-type rubber adhesive has a problem of toxicity to a human body due to a solvent and a problem of fire. Therefore, a moisture-curable contact type adhesive using a polymer compound having a reactive silicon group in the molecule without using a solvent has been proposed as described in JP-A-3-263478.

The polymer compound having a reactive silicon group which constitutes the contact type adhesive described in the above publication is a (meth) acrylate copolymer having a substantially reactive silicon group and an oxyalkylene polymer having a reactive silicon group. The (meth) acrylate copolymer is a copolymer of two kinds of (meth) acrylates having different carbon numbers and a (meth) acrylalkoxysilane and / or a mercaptoalkoxysilane, although it is composed of a united product. However, this adhesive containing a polymer compound having a reactive silicon group as a component requires a long time to develop tack, and cannot be used as a substitute for the existing rubber contact adhesive.

On the other hand, the adhesive used in the field construction of building interior materials and the adhesive used to bond the rubber and concrete used to stop the water at the concrete joint of the tunnel are used in the room or in the tunnel. In addition to being non-BTX (benzene, toluene, xylene) as a countermeasure against sick house disease, there is a demand for a contact-type adhesive that is solvent-free and has a long possible bonding time from the viewpoint of environmental problems and fire prevention.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a urethane resin contact type in which the time to tack development is short, the tack is strong, the adhesion strength immediately after bonding is large, the tack range is long, and the bonding time is long. The purpose is to provide an adhesive. Another object of the present invention is to provide a urethane resin-based contact adhesive which is suitable for contact adhesion and has excellent adhesion to a wide range of non-porous materials such as metals, plastics and rubbers.

[0006]

[Means for Solving the Problems] In order to achieve the above object, the inventors of the present invention have conducted extensive studies and as a result, found that the main chain is a polyoxyalkylene polymer containing at least polyoxyethylene, and It has been found that those containing a urethane resin having a -RN-CO-NH- bond (R is a specific substituent) and a hydrolyzable silicon group and a tackifying resin as components can achieve the object of the present invention. The present invention has been reached.

That is, the present invention is a polyoxyalkylene polymer having a main chain containing at least polyoxyethylene, and having a group represented by the following general formula (1) and the following general formula (2) in its molecule. The gist is a urethane resin contact adhesive containing the urethane resin (A) and the tackifying resin (B) as components.

[0008]

[Chemical 7]

[Chemical 8]

However, R ¹ is the following general formula (3), the following general formula (4), the following general formula (5) or a substituted or unsubstituted organic group having 1 to 20 carbon atoms, and R ² is the carbon number. 1 to 20 substituted or unsubstituted organic groups, X represents a hydroxyl group or a hydrolyzable group, and n represents 0, 1 or 2.

[0010]

[Chemical 9]

[Chemical 10]

[Chemical 11]

However, R ³ is a hydrogen atom or --COOR.
¹⁰ , R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is —COO.
R ¹¹ or a nitrile group, R ⁶ is a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms, and R ⁷ is a molecular weight of 500.
The following organic groups which may contain a silicon atom are represented by R ⁸ and R ⁹
Represents the above general formula (3) or the following general formula (6), and R ¹⁰ and R ¹¹ each represent an organic group having a molecular weight of 500 or less.

[0012]

[Chemical 12]

The present invention further comprises a vinyl polymer (C) obtained by polymerizing the urethane resin (A), the tackifying resin (B) and the polymerizable vinyl group-containing monomer (compound (a)). The gist is the urethane resin-based contact adhesive that is contained as.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The urethane resin contact adhesive of the present invention is a polyoxyalkylene polymer having a main chain containing polyoxyethylene, and the general formula (1) and the general formula ( The urethane resin (A) having a group represented by 2) and the tackifying resin (B) are contained as components.

R ¹ , R ² and n in the general formula (1) and the general formula (2) representing the urethane resin (A)
Is as described above, and examples of the hydrolyzable group of X include an alkoxy group, an acetoxy group, an oxime group, and the like.
An alkoxy group is particularly preferable. The urethane resin (A) is a known resin, typically a polyoxyalkylene polymer having a main chain containing at least polyoxyethylene, and having a hydroxyl group, a mercapto group and a primary amino group in its molecule, or A urethane prepolymer (D) is produced by reacting a compound (compound (b)) having one or more groups selected from secondary amino groups with a polyisocyanate compound (compound (c)), and further the urethane prepolymer ( It can be produced by reacting D) with a compound represented by the following general formula (7) (compound (d)).

The polyoxyalkylene polymer used as the raw material of the compound (b) is preferably a hydroxyl group-terminated product produced by reacting an initiator with a monoepoxide or the like in the presence of a catalyst. As the initiator, a hydroxy compound having one or more hydroxyl groups can be used. As the monoepoxide, ethylene oxide is an essential component, and propylene oxide, butylene oxide, hexylene oxide, etc., tetrahydrofuran, etc. can be used together. Examples of the catalyst include alkali metal catalysts such as potassium compounds and cesium compounds, complex metal cyanide compound complex catalysts, and metal porphyrin catalysts. The complex metal cyanide compound complex catalyst is preferably a complex containing zinc hexacyanocobaltate as a main component, an ether and / or alcohol complex. As the composition of the ether and / or alcohol complex, the composition essentially described in JP-B-46-27250 can be used. As the ether, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme) and the like are preferable, and glyme is particularly preferable from the viewpoint of handling during production of the complex. As the alcohol, for example, those described in JP-A-4-145123 can be used, but especially tert-
Butanol is preferred.

The above raw material polyoxyalkylene polymer has a number average molecular weight of 500 to 30,000, particularly 2,
It is preferable to use those of 000 to 20,000.

The raw material polyoxyalkylene polymer preferably has two or more functional groups, specifically, polyoxyethylene or at least 1% by mass of polyoxyethylene.
Including polyoxypropylene, polyoxybutylene,
Examples thereof include copolymers of polyoxyhexylene, polyoxytetramethylene and the like. A preferable raw material polyoxyalkylene polymer is a polyoxypropylene polyol having 2 to 6 valences, particularly polyoxypropylene diol and polyoxypropylene triol, and the total amount of oxypropylene and oxyethylene in the polyoxypropylene polyol is 100 parts by mass. The amount of oxyethylene is 1 part by mass or more, preferably 3 to 80 parts by mass. The compound (b) is commercially available, and they can be used in the present invention.

Examples of the isocyanate compound (compound (c)) used when the urethane prepolymer (D) is reacted with the compound (b) include diisocyanate compounds, polyisocyanate compounds other than diisocyanate compounds, and the like. To be Examples of the diisocyanate compound include aliphatic, alicyclic, araliphatic, aromatic diisocyanate compounds and the like. Specific examples thereof will be given below.

Aliphatic diisocyanate compound: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene Diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate and the like. Alicyclic diisocyanate compound: 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate,
3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-
Cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and the like. Aromatic aliphatic diisocyanate compound: 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanate) -1-Methylethyl) benzene or a mixture thereof and the like. Aromatic diisocyanate compound: m-phenylene diisocyanate, p-phenylene diisocyanate, 4,
4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate,
4,4'-diphenyl ether diisocyanate and the like.

Examples of the polyisocyanate compound excluding the diisocyanate compound include aliphatic, alicyclic, araliphatic and aromatic polyisocyanate compounds. Specific examples thereof will be given below.

Aliphatic polyisocyanate compound: lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanatomethyl octane, 1,3,3. 6-triisocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyloctane and the like. Alicyclic polyisocyanate compound: 1,3,5-triisocyanate cyclohexane, 1,3,5-trimethylisocyanate cyclohexane, 3-isocyanate-
3,3,5-Trimethylcyclohexyl isocyanate, 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo [2,2,1] heptane, 2- (3-isocyanatopropyl) -2, 6
-Di (isocyanatomethyl) -bicyclo [2,2,2
1] Heptane, 5- (2-isocyanatoethyl) -2
-Isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 6- (2
-Isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) ) -Bicyclo [2,2,1] heptane, 6- (2-isocyanatoethyl) -2- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane and the like. Aromatic aliphatic polyisocyanate compound: 1,3,5-triisocyanate methylbenzene and the like. Aromatic polyisocyanate compound: triphenylmethane-4,4 ', 4 "-triisocyanate, 1,3,5-
Triisocyanate benzene, 2,4,6-triisocyanate toluene, 4,4′-diphenylmethane-2,
2 ', 5,5'-tetraisocyanate and the like. Other polyisocyanate compounds: Diisocyanates containing a sulfur atom such as phenyldiisothiocyanate.

The compound (d) to be reacted with the urethane prepolymer (D) is represented by the following general formula (7).

[0024]

[Chemical 13]

However, R ¹ , R ² , X and n have the same meanings as defined above, and Y is a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms, the following general formula (8): Alternatively, the following general formula (9) is shown respectively.

[0026]

[Chemical 14]

[Chemical 15]

However, R ³ , R ⁴ , R ⁵ , R ⁶ R and R ⁷
Is as defined above, and R ¹² and R ¹³ have 1 carbon atom.
It shows 10 substituted or unsubstituted divalent organic groups.

Compound (d) represented by the above general formula (7)
Specific examples of N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N- (n-butyl) -γ-
Aminopropyltrimethoxysilane, N- (n-butyl) -γ-aminopropylmethyldimethoxysilane, N
-Ethylaminoisobutyltrimethoxysilane, N-methylaminopropylmethyldimethoxysilane, N-methylaminopropyltrimethoxysilane, bis (trimethoxysilylpropyl) amine and the like can be mentioned, but they can be produced by the following method.

(1) R ¹ is represented by the above general formula (3),
Compound in which Y is a divalent organic group Primary amino group and hydrolyzable group-containing silicon group or hydroxyl group-containing silicon group (preferably hydrolyzable group-containing silicon group)
A compound (compound (e)) having one of each of the above, and one or more selected from an α, β-unsaturated carbonyl compound (compound (f)), a maleic acid diester (compound (g)) and acrylonitrile in a chemical equivalent thereto Method of reacting two or more kinds (2) R ¹ is a compound represented by the above general formula (3), and Y is a compound represented by the above general formula (8). Primary amino group, secondary amino group and hydrolysis Compound (compound (h)) each having one functional group-containing silicon group or one hydroxyl group-containing silicon group (preferably a hydrolyzable group-containing silicon group), and a primary amino group and a secondary compound in the compound (h) Method (3) of reacting an amino group with one or more kinds selected from chemical equivalents of compound (f), compound (g) and acrylonitrile, R ¹ is represented by the above general formula (3), and Y is the above. Compound represented by general formula (9) Compound (h), the compound (h) the primary amino group and a chemical equivalent of the compound in (f), after reaction of the compound (g) and one or more selected from acrylonitrile,
Compound (h) wherein R ⁷ of the secondary amino group and a chemical equivalent of
Method (4) of reacting monoisocyanate compound (compound (i)) represented by NCO (R ⁷ has the same meaning as above), R ¹ is represented by the above general formula (4), and Y is a divalent organic group. A method of reacting the compound (h) with the compound (h) with a primary amino group in the compound (h) and a chemical equivalent of the compound (i), R ¹ is represented by the above general formula (5), and R ⁸ and R ⁹ in the general formula (5) are represented by the above general formula (3),
A compound compound (h) in which Y is a divalent organic group, and a primary amino group in the compound (h) and 2
Method (6) of reacting one or more selected from chemical equivalents of compound (f), compound (g) and acrylonitrile, R ¹ is represented by the above general formula (5) and is represented by the general formula (5) Wherein R ⁸ is represented by the above general formula (3), R ⁹ is represented by the above general formula (6), and Y is a divalent organic group, and a compound (h) After reacting the primary amino group with one or more compounds selected from the chemical equivalents of compound (f), compound (g) and acrylonitrile,
A method of reacting the secondary amino group produced by this reaction with a chemical equivalent of the compound (i).

Examples of the compound (e) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane and aminophenyltrimethoxysilane. Can be mentioned.

Examples of the compound (f) include (meth) acrylic compounds, vinyl ketone compounds, vinyl aldehyde compounds and other compounds. As the (meth) acrylic compound, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate,
t-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth)
Acrylate, 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, stearyl (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol (meth ) Acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, Carboxymethyl ethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, dicyclopentadienyl
(Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, diacetone (meth) acrylate, iso Butoxymethyl (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformaldehyde, N, N-dimethylacrylamide, t-octylacrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7 -Amino-3,7-dimethyloctyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N'-dimethylaminopropyl (meth) acrylamide, acryloylmo Other such Hollin, Toagosei Chemical Industry Co., Ltd. under the trade name: Aronix M-102, M-1
11, M-114, M-117, trade name manufactured by Nippon Kayaku Co., Ltd .: Kayahard TC110S, R629, R644,
Trade name: Viscoat 3700 manufactured by Osaka Organic Chemical Co., Ltd., and the like.

Further, trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4
-Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate Tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, epoxy obtained by adding (meth) acrylate to glycidyl ether of bisphenol A (meth). ) A polyfunctional compound such as acrylate and a commercial product of the polyfunctional compound manufactured by Mitsubishi Chemical Co., Ltd .: trade name: UPIMER UV, SA1002, SA2
007, product name of Osaka Organic Chemical Company: Viscote 70
0, product name of Nippon Kayaku Co., Ltd .: Kayahard R604, D
PCA-20, DPCA-30, DPCA-60, DP
CA-120, HX-620, D-310, D-33
0, product name of Toagosei Chemical Industry Co., Ltd .: Aronix M-
210, M-215, M-315, M-325 and the like.

In addition to the above compounds, γ-methacryloxypropyltrimethoxysilane having an alkoxysilyl group, γ-methacryloxypropyltriethoxysilane,
γ-methacryloxymethyldimethoxysilane, γ-methacryloxymethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxymethyldimethoxysilane and the like can be mentioned.

Examples of vinyl ketone compounds include vinyl acetone, vinyl ethyl ketone, vinyl butyl ketone, and the like.
Examples of vinyl aldehyde compounds include acrolein, methacrolein, and crotonaldehyde, and examples of other compounds include maleic anhydride, itaconic anhydride, itaconic acid, crotonic acid, N-methylol acrylamide, diacetone acrylamide, N- [3- (Dimethylamino) propyl] methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-
Examples thereof include t-octyl acrylamide and N-isopropyl acrylamide.

In addition to the above compounds, compounds containing a fluorine atom, a sulfur atom or a phosphorus atom therein are also included. Examples of the compound containing a fluorine atom include perfluorooctylethyl (meth) acrylate and trifluoroethyl (meth) acrylate, and examples of the compound containing a phosphorus atom include (meth) acryloxyethylphenyl acid phosphate.

Among the above-mentioned compounds (f), methyl acrylate, ethyl acrylate, propyl acrylate, from the standpoints of easy reaction and wide commercial availability.
Butyl acrylate, t-butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate and the like are preferable. Of these, methyl acrylate and ethyl acrylate are particularly preferable for imparting fast curing property, and 2-ethylhexyl acrylate and lauryl acrylate are particularly preferable for imparting flexibility. The compound (f) may be used alone or in combination of two or more.

As the compound (g) (maleic acid diester), dimethyl maleate, diethyl maleate, dibutyl maleate, di2-ethylhexyl maleate,
Examples thereof include dioctyl maleate, and these can be used alone or in combination of two or more. Among these, the ease of reaction,
Dimethyl maleate, diethyl maleate, dibutyl maleate, and di2-ethylhexyl maleate are preferred because they are widely marketed and easily available. The compound (g) can be used alone or in combination of two or more.

As the compound (h), N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-
β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ
-Aminopropylmethyldiethoxysilane, N-3-
[Amino (dipropyleneoxy)] aminopropyltrimethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (6-aminohexyl)
Aminopropyltrimethoxysilane, N- (2-aminoethyl) -11-aminoundecyltrimethoxysilane, other special aminosilane manufactured by Shin-Etsu Chemical Co., Ltd.,
Product name: KBM6063, X-12-896, KBM5
76, X-12-565, X-12-580, X-12
-5263, KBM6123, X-12-575, X-
12-562, X-12-5202, X-12-520
4, KBE9703 and the like.

Among the above compounds (h), N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, in view of easiness of reaction, wide commercial availability and availability.
N-β (aminoethyl) -γ-aminopropyltriethoxysilane and N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane are preferable.

Examples of the compound (i) include ethyl isocyanate, n-hexyl isocyanate, n-dodecyl isocyanate, p-toluenesulfonyl isocyanate, n-hexyl isocyanate, benzyl isocyanate, 2-methoxyphenyl isocyanate and the like. Besides, isocyanate silanes such as Shin-Etsu Chemical Co., Ltd. product name: KBM9007 (γ-isocyanatopropyltrimethoxysilane) and the like can be mentioned.

The method of reacting the compound (b) with the compound (c) to obtain the urethane prepolymer (D) is a usual method of reacting a polyol compound with a polyisocyanate compound to produce a urethane prepolymer. You can do according to. Moreover, the method of making the urethane resin (A) by reacting the compound (d) with the urethane prepolymer (D) is at 50 to 100 ° C. for 30 minutes to 3
Done on time.

The urethane resin contact type adhesive of the present invention contains the above urethane resin (A) and tackifying resin (B) as components. Tackifying resin (B)
There is no particular limitation, and those which are normally used at room temperature regardless of whether they are solid or liquid can be used. Specific examples include phenolic resins and modified phenolic resins (for example,
Cashew oil modified phenolic resin, tall oil modified phenolic resin, etc.), terpene phenolic resin, xylene-
Phenol resin, cyclopentadiene-phenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C ₅ Hydrocarbon resin, C ₉ hydrocarbon resin, C ₅ C ₉ hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin,
Examples thereof include terpene resins and DCPD resins. These may be used alone or in combination of two or more. Among the above tackifying resins, terpene phenol resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, styrene copolymer resin, C ₉ hydrocarbon resin, hydrogenated petroleum resin and terpene resin are particularly preferred. It is preferable because it has good solubility and good adhesive properties.

When the tackifying resin (B) is blended with the urethane resin (A), the blending ratio is 5 to 2 with respect to 100 parts by mass of the urethane resin (A).
The amount is 00 parts by mass, preferably 10 to 100 parts by mass. If the compounding amount of the tackifying resin (B) is less than 5 parts by mass, the effect of lengthening the initial tack strength and the tack range is not sufficient, and if it exceeds 200 parts by mass, the heat resistance decreases and the viscosity increases. Resulting in.

The adhesive containing the urethane-based resin (A) and the tackifying resin (B) as the components shows good contact adhesiveness, but further, a polymerizable vinyl group-containing monomer (compound (a)) is polymerized. By using the vinyl polymer (C) obtained in combination with the above, a urethane resin contact adhesive having a superior tack and a long tack range can be obtained.

The vinyl polymer (C) is a polymer of the compound (a) which is a polymerizable vinyl group-containing monomer, and the compound (a) includes acrylic acid, methacrylic acid, acrylic acid ester or methacrylic acid ester ( Hereinafter, these are referred to as (meth) acrylates), styrene compounds, acrylonitrile, α-methylacrylonitrile,
2,4-dicyanobutene-1, vinylpyrrolidone, vinylcarbazole, 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl maleate, 2-methacryloyloxyethyl phthalate, 2-methacryloyloxyethyl hexahydrophthalate, acrylamide, Methacrylamide, vinyl glycidyl ether,
Allyl glycidyl ether, methacryl glycidyl ether, vinyl chloride, vinyl acetate, vinyl propionate,
Butadiene, isoprene, chloroprene; olefins other than these, unsaturated esters, halogenated olefins, vinyl ethers and the like.

As the (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate,
n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate,
Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, Hexadecyl (meth) acrylate, octadecyl (meth) acrylate, etc. Alkyl ester of acrylic acid or methacrylic acid whose alkyl group has 1 to 20 carbon atoms; cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate,
Phenyl acrylate, phenyl methacrylate, isobornyl acrylate, isobornyl methacrylate,
Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, tert-butylaminoethyl acrylate, tert-butylaminoethyl methacrylate, cyclohexylaminoethyl acrylate, cyclohexylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, tetrahydrofuran acrylate, tetrahydrofuran methacrylate, allyl acrylate, allyl Methacrylate, 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 2-hydroxy-3
-Phenoxypropyl acrylate, 2-hydroxy-
3-phenoxypropyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trade name: M-110 manufactured by Toagosei Co., Ltd.
And M-111, Shell Chemical Company trade name: Veova 9 and Veova 10, trifluoroethyl methacrylate, and the like.

Examples of styrene compounds include styrene, vinyltoluene, divinylbenzene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene and p-methoxystyrene. . Among these, acrylonitrile, styrene, glycidyl methacrylate, carbon number 1
-20 alkyl esters of acrylic acid or methacrylic acid are preferred. These polymerizable vinyl group-containing monomers (compound (a)) are not limited to one type, and two or more types can be used.

As the compound (a), a vinyl group-containing monomer having a hydrolyzable silicon group can also be used. As the vinyl group-containing monomer, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, tris (2-methoxyethoxy) vinylsilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane. , 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and the like. Among these, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropyl Trimethoxysilane and 3-methacryloyloxypropyltrimethoxysilane are particularly preferred.

As the method of polymerizing the compound (a), any of known methods such as radical polymerization, anionic polymerization and cationic polymerization, which are commonly used for the polymerization of these monomers, can be adopted. In particular, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'- Azobis (2-methyl-4-trimethoxysilylpentonitrile), 2,2'-azobis (2-methyl-4-methyldimethoxysilylpentonitrile), Wako Pure Chemical Industries, Ltd. product name: VA-046B, V
A-057, VA-061, VA-085, VA-08
6, VA-096, V-601, V-65 and VAm-
Azo compounds such as 110, benzoyl peroxide, t-
Alkyl peroxy ester, acetyl peroxide,
A radical polymerization method performed in the presence of a peroxide polymerization initiator such as diisopropyl peroxycarbonate is suitable.
At this time, lauryl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, thio-β-naphthol, thiophenol, n-butyl mercaptan, ethyl thioglycolate, isopropyl mercaptan, t-butyl mercaptan, γ The polymerization can be carried out in the presence of a chain transfer agent such as trimethoxysilylpropyl disulfide. The polymerization reaction is preferably carried out at a temperature of 20 to 200 ° C., particularly 50 to 150 ° C. for several hours to several tens hours. Also, xylene, toluene, acetone, methyl ethyl ketone, ethyl acetate,
The polymerization can be carried out in the presence of a solvent such as butyl acetate. After completion of the polymerization, these solvents may be removed by a method such as vacuum distillation, if necessary, and the urethane resin (A) and the tackifying resin (B) may be removed without removing these solvents.
You may mix with others.

When the vinyl polymer (C) is blended with the urethane resin (A) and the tackifying resin (B), the blending ratio is the urethane resin (A) and the tackifying resin (B) 1
The vinyl polymer (C) is 5 to 500 parts by weight, preferably 10 to 200 parts by weight, per 00 parts by weight. When the blending amount of the vinyl polymer (C) is less than 5 parts by mass, the effect of improving the tack strength, the effect of lengthening the tack range, the effect of extending the bonding time and the strength when the open time is long are sufficient. If it exceeds 500 parts by mass, the cohesive force will be insufficient and the initial settability will be poor.

The urethane resin-based contact adhesive compounded with the vinyl polymer (C) of the present invention is a urethane resin (A), a tackifying resin (B) and a vinyl polymer (C).
(1) The above compound (a) in the urethane resin (A) and the tackifying resin (B)
In the above method for preparing the urethane-based resin (A), after polymerizing the compound (a) in the compound (b), the compound (c), and further the compound (d). In the above method for preparing the urethane resin (A), the compound (b) and the compound (c) are reacted to obtain a urethane prepolymer (D). It can also be prepared by a method of polymerizing the compound (a) in (D) and then reacting with the compound (d).

The urethane resin contact adhesive of the present invention comprises the urethane resin (A) and the tackifying resin (B), and further the urethane resin (A), the tackifying resin (B) and the above. Although the vinyl polymer (C) is contained as an active ingredient, a curing catalyst, a filler, and various additives may be contained in addition to these active ingredients, if necessary.

As the above-mentioned curing catalyst which can be contained as required, an organic tin compound, a metal complex, a basic compound, an organic phosphorus compound and water (humidity in the air) can be used. Specifically, as the organic tin compound, dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyltin diacetylacetate, dibutyltin diversate, dibutyltin oxide, dibutyltin oxide and A reaction product with a phthalic acid diester, trade names: U700, U700ES, U303 and the like manufactured by Nitto Kasei Co., Ltd. Examples of the metal complex include titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate, lead octylate, lead naphthenate, nickel naphthenate, cobalt naphthenate, bismuth octylate, and carboxylic acids such as bismuth versatate. Examples thereof include metal acetylacetonate complexes such as metal salts, aluminum acetylacetonate complexes, and vanadium acetylacetonate complexes. Examples of the basic compound include aminosilanes such as γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane, quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride, and DABCO manufactured by Sankyo Air Products Co., Ltd. (Registered trademark) series, DAB
CO BL series, 1,8-diazabicyclo [5.
4.0] linear or cyclic tertiary amines containing a plurality of nitrogens such as undec-7-ene and quaternary ammonium salts. Examples of the organic phosphorus compound include monomethyl phosphoric acid, di-n-butyl phosphoric acid, triphenyl phosphate and the like. The mixing ratio of the curing catalyst is 0.01 to 1 per 100 parts by mass of the active ingredient of the urethane resin contact adhesive.
It is 0 part by mass.

Examples of the filler include fumed silica, calcium carbonate, magnesium carbonate, clay, talc, silica and various balloons.

Examples of various additives include plasticizers, additives, solvents and dehydrating agents. As the plasticizer, phthalic acid esters such as dioctyl phthalate and dibutyl phthalate, and aliphatic carboxylic acid esters such as dioctyl adipate and dibutyl sebacate can be used. As the additives, antiaging agents, thixotropic agents, ultraviolet absorbers, pigments, various tackifiers,
Examples thereof include silane coupling agents, titanate coupling agents, aluminum coupling agents, and epoxy resins such as bisphenol A type and bisphenol F type. As the silane coupling agent, aminosilane is particularly preferable. As the solvent, any solvent may be used as long as it has good compatibility with the urethane resin contact adhesive and the like and has a water content of 500 ppm or less. Examples of the dehydrating agent include quicklime, orthosilicate, anhydrous sodium sulfate, zeolite, methyl silicate, ethyl silicate, various alkylalkoxysilanes, various vinylalkoxysilanes, and the like.

[0056]

EXAMPLES The present invention will be described in detail below with reference to examples.

(Example 1) (1) 1,000 g of polyoxypropylene diol having a number average molecular weight of 4,000 (Takelac P-28, trade name: manufactured by Takeda Pharmaceutical Co., Ltd.) and having a number average molecular weight of 4,000 1,000 g of 25% polyoxyethylene addition type polyoxypropylene diol (PML-5005, trade name: manufactured by Asahi Glass Co., Ltd.) at the terminal, and Sumidule T-80 (trade name:
174.2 g of Sumitomo Bayer Urethane Co., Ltd. tolylene diisocyanate) was placed in a reaction vessel and reacted at 90 ° C. for 3 hours under stirring in a nitrogen atmosphere to obtain a urethane prepolymer (PUR-1). (2) KBM903 (Product name: Shin-Etsu Chemical Co., Ltd., γ-
179.3 g of aminopropyltrimethoxysilane),
Methyl acrylate was mixed at a ratio of 86.1 g, and 23
The reaction was performed at 7 ° C for 7 days to obtain a reaction product (AS-1). (3) KBM902 (trade name: Shin-Etsu Chemical Co., Ltd., γ-
Aminopropylmethyldimethoxysilane) 163.3
g and 2-ethylhexyl acrylate were mixed at a ratio of 184.3 g and reacted at 23 ° C. for 7 days to give a reaction product (AS
-2) was obtained. (4) 1,00 of urethane prepolymer (PUR-1)
0 g, reaction product (AS-1) 61 g, reaction product (AS-)
2) was put in a reaction vessel at a rate of 80 g, and under a nitrogen atmosphere,
The reaction was carried out for 1 hour at 90 ° C. with stirring to obtain a liquid urethane resin (1). (5) 500 g of the urethane resin (1) was placed in a reaction vessel and heated to 100 ° C. under a nitrogen atmosphere to give 250 g of methyl methacrylate and 250 g of n-lauryl methacrylate.
50 g of KBM503 (trade name: γ-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.),
5 g of KBM803 (trade name: γ-mercaptopropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.), 5 g of lauryl mercaptan and 5 of azobisisobutyronitrile
The mixed solution mixed at a ratio of g was added dropwise over 5 hours,
Further, the mixture was reacted at 100 ° C. for 2 hours to obtain a mixture (1-1) of vinyl polymer and urethane resin. (6) the mixture (1-1) to 1,000 g, neo polymer S (trade name: Nippon Petrochemicals Co., Ltd., C ₉ hydrocarbon resin) and 300g and NS400 (trade name: manufactured by Nitto Funka Kogyo Co., carbonate (Calcium) at a rate of 500 g was put in a planetary mixer and heated and dehydrated at 100 ° C. under reduced pressure.
Cool to room temperature, 50 g of KBM903, KBM403
(Product name: Shin-Etsu Chemical Co., Ltd., γ-glycidoxypropyltrimethoxysilane) 30 g and Stan No. 91
8 (trade name: Sankoki Gosei Co., Ltd., organotin catalyst) 10 g
Kneading was performed to obtain a urethane resin contact adhesive.

(Example 2) (1) 1,00 of urethane prepolymer (PUR-1)
0 g and the reaction product (AS-2) were put in a reaction container at a ratio of 160 g and reacted at 90 ° C. for 1 hour under a nitrogen atmosphere with stirring to obtain a liquid urethane resin (2). (2) A mixture (2) of a vinyl polymer and a urethane resin was obtained in the same manner as in (5) of Example 1 except that the urethane resin (2) was used instead of the urethane resin (1). It was (3) 700 g of the above mixture (2), ESGX-340
6a (trade name: Asahi Glass Co., Ltd., vinyl group-containing monomer (mixture of acrylonitrile and styrene) polymer, molecular terminal trimethoxysilyl type modified silicone resin) 30
0 g, Alcon P-70 (trade name: manufactured by Arakawa Chemical Industries,
Hydrogenated petroleum resin) 300 g and NS400 5
Put in a planetary mixer at a rate of 00g, and under reduced pressure 1
After dehydration by heating at 00 ° C, cool to room temperature and use KBM90.
3 for 50 g, KBM403 for 30 g and Stan No. 9
10 g of 18 was kneaded to obtain a urethane resin contact adhesive.

(Example 3) (1) 1,00 of urethane prepolymer (PUR-1)
0 g and the reaction product (AS-1) were put in a reaction container at a ratio of 122 g and reacted at 90 ° C. for 1 hour under a nitrogen atmosphere with stirring to obtain a liquid urethane resin (3). (2) A mixture (3) of a vinyl polymer and a urethane resin was obtained in the same manner as in (5) of Example 1 except that the urethane resin (3) was used instead of the urethane resin (1). It was (3) 500 g of the mixture (3), 500 g of MA440 (trade name: polymer of (meth) acryloyl group-containing monomer, modified silicone resin of molecular terminal methyldimethoxysilyl type, manufactured by Kanebuchi Chemical Co., Ltd.), YS T-100
(Product name: Yasuhara Chemical Co., terpene-phenol copolymer resin) 300 g and NS400 at a ratio of 500 g were put in a planetary mixer, heated and dehydrated under reduced pressure at 100 ° C., then cooled to room temperature, and KBM903 50 was added.
g, 30 g of KBM403 and Stan No. 918 to 1
0 g was kneaded to obtain a urethane resin contact adhesive.

(Example 4) Urethane prepolymer (PU
R-1) 1,000 g, super ester A-75
(Product name: Arakawa Chemical Industry Co., Ltd., special rosin ester resin) 300g and NS400 at a ratio of 500g were put in a planetary mixer, heated and dehydrated under reduced pressure at 100 ° C, then cooled to room temperature, 50g of KBM903, KBM.
30 g and Stan No. 10 g of 918 was kneaded to obtain a urethane resin contact adhesive.

(Example 5) 500 g of a mixture (1-1) of a vinyl polymer and a urethane resin, and 500 g of SAT200 (trade name: Kanegafuchi Chemical Industry Co., Ltd., a modified silicone resin of molecular terminal methyldimethoxysilyl type). , Pine Crystal KE-100 (trade name: hydrogenated rosin ester resin manufactured by Arakawa Chemical Industry Co., Ltd.) and NS400.
Was added to a planetary mixer at a rate of 500 g, and was dehydrated by heating at 100 ° C. under reduced pressure, then cooled to room temperature, and KBM was added.
903 50g, KBM403 30g and Stan N
o. 10 g of 918 was kneaded to obtain a urethane resin contact adhesive.

Example 6 The urethane resin (1) was added to 50
0g, SAT200 500g, Nikanol HP70
(Product name: Mitsubishi Gas Chemical Co., Inc., xylene resin) 300
g and NS400 in a ratio of 500 g in a planetary mixer, heated and dehydrated under reduced pressure at 100 ° C., and then cooled to room temperature, 50 g of KBM903 and 30 g of KBM403.
g and Stan No. 10 g of 918 was kneaded to obtain a urethane resin contact adhesive.

Example 7 (1) 174.2 g of Sumidule T-80 was placed in a reaction vessel, and the reaction product (AS-1) was stirred under a nitrogen atmosphere while stirring.
A mixture of 132.7 g and the reaction product (AS-2) (173.8 g) was added dropwise over 3 hours and further reacted at room temperature for 1 hour to obtain a reaction product (IS-1). (2) 1,000 g of Takelac P-28, PML-5
005 for 1,000 g and the reaction product (IS-1) for 480
A liquid urethane resin (4) was obtained by placing the mixture in a reaction vessel at a rate of g and reacting at 90 ° C. for 3 hours under stirring in a nitrogen atmosphere. (3) A mixture (4) of a vinyl polymer and a urethane resin was obtained in the same manner as in (5) of Example 1 except that the urethane resin (4) was used instead of the urethane resin (1). It was (4) 500 g of the above mixture (4), FTR6100
(Product name: styrene-aliphatic hydrocarbon copolymer resin manufactured by Mitsui Chemicals, Inc.) and NS400 at a ratio of 500 g were put in a planetary mixer, heated and dehydrated at 100 ° C. under reduced pressure, and then cooled to room temperature, KBM903. 50g,
30 g of KBM403 and Stan No. 10g of 918
Kneading was performed to obtain a urethane resin contact adhesive.

Example 8 (1) 500 g of the urethane resin (1) was placed in a reaction vessel and heated to 100 ° C. under a nitrogen atmosphere to give 250 g of methyl methacrylate and 250 g of n-lauryl methacrylate.
g, 5 g of lauryl mercaptan and 5 g of azobisisobutyronitrile were added dropwise over 5 hours, and the mixture was further reacted at 100 ° C. for 2 hours to react the mixture of vinyl polymer and urethane resin (1 -2) was obtained. (2) 1,000 g of the above mixture (1-2), YP90
LL (trade name: Yasuhara Chemical Co., terpene-phenol copolymer) 300 g and NS400 500 g
In a planetary mixer at a rate of 100 ℃ under reduced pressure
After heating and dehydration with, cool to room temperature and add KBM903 to 5
0 g, KBM403 30 g and Stan No. 10 g of 918 was kneaded to obtain a urethane resin contact adhesive.

Example 9 (1) 500 g of the urethane resin (1) was placed in a reaction vessel and heated to 100 ° C. in a nitrogen atmosphere to give 250 g of methyl methacrylate and 250 g of lauryl methacrylate.
50 g of KBM503, 5 g of KBM803, 5 g of lauryl mercaptan and 2,2′-azobis (2-methyl-4-trimethoxysilylpentonitrile) in a proportion of 5 g were added dropwise over 5 hours, and further, 1
The mixture was reacted at 00 ° C for 2 hours to obtain a mixture (1-3) of a vinyl polymer and a urethane prepolymer. (2) 1,000 g of the above mixture (1-3), FTR7
100 (trade name: styrene-α-methylstyrene-aliphatic hydrocarbon copolymer resin manufactured by Mitsui Chemicals, Inc.) and 300 g of NS400 were put in a planetary mixer at a ratio of 500 g, and after heating and dehydrating at 100 ° C. under reduced pressure, After cooling to room temperature, 50 g of KBM903, 30 g of KBM403 and Stan No. 10 g of 918 was kneaded to obtain a urethane resin contact adhesive.

Example 10 (1) 500 g of the urethane resin (1) was placed in a reaction vessel and heated to 100 ° C. under a nitrogen atmosphere to give 250 g of methyl methacrylate and 250 g of n-lauryl methacrylate.
g, 50 g of KBM503, 10 g of γ-trimethoxysilylpropyl disulfide (DSPTMS) and 5 g of azobisisobutyronitrile were added dropwise over 5 hours, and the mixture was further reacted at 100 ° C. for 2 hours. Mixture of vinyl polymer and urethane prepolymer (1-
4) was obtained. (2) 1,000 g of the mixture (1-4), 300 g of Nikanol HP100 (trade name: xylene resin manufactured by Mitsubishi Gas Chemical Co., Inc.) and NS400 in a planetary mixer at a ratio of 500 g, and the mixture was placed under reduced pressure at 100 ° C. After dehydration by heating, cool down to room temperature, 50 g of KBM903, KBM
30 g and Stan No. 10 g of 918 was kneaded to obtain a urethane resin contact adhesive.

(Example 11) (1) KBM602 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd., N-
β (aminoethyl) -γ-aminopropylmethyldimethoxysilane) 206.4 g, methyl acrylate 1
The reaction product (AS-3) was obtained by reacting at 72.2 g for 7 days at 23 ° C. (2) Add urethane prepolymer (PUR-1) to 1,00
0 g, KBM573 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd., N-
59 g of phenyl-γ-aminopropyltrimethoxysilane) and 87 g of the reaction product (AS-3) were placed in a reaction vessel and reacted under nitrogen atmosphere at 90 ° C. for 1 hour with stirring to obtain a liquid urethane system. Resin (5) was obtained. (3) A mixture (5) of a vinyl polymer and a urethane resin was obtained in the same manner as in (5) of Example 1 except that the urethane resin (5) was used instead of the urethane resin (1). It was (4) 1,000 g of the above mixture (5), Nikanol L
L (trade name: Mitsubishi Gas Chemical Co., Inc., xylene resin) 30
0 g and NS400 were put in a planetary mixer at a ratio of 500 g, heated and dehydrated at 100 ° C. under reduced pressure, and then cooled to room temperature, 50 g of KBM903 and 3 of KBM403.
0 g and Stan No. 10 g of 918 was kneaded to obtain a urethane resin contact adhesive.

Example 12 (1) 100 parts of urethane prepolymer (PUR-1) was added.
0g, DYNASYLAN 1189 (trade name: Degussa-
Huls AG, N- (n-butyl) -γ-aminopropyltrimethoxysilane) 59 g, reaction product (AS-4)
Was put in a reaction vessel at a rate of 87 g, and reacted at 90 ° C. for 1 hour while stirring in a nitrogen atmosphere to obtain a liquid urethane resin (6). (2) A mixture (6) of a vinyl polymer and a urethane resin was obtained in the same manner as in (5) of Example 1 except that the urethane resin (6) was used instead of the urethane resin (1). It was (3) 1,000 g of the above mixture (6), YS oil D
300 g of A (trade name: Yasuhara Chemical Co., Ltd. low polymerization resin) and NS400 of 500 g were put in a planetary mixer, and dehydrated by heating at 100 ° C. under reduced pressure and then cooled to room temperature, 50 g of KBM903 and KBM903.
30 g and Stan No. 10 g of 918 was kneaded to obtain a urethane resin contact adhesive.

Example 13 (1) 179.3 g of KBM903 and 144.1 g of dimethyl maleate were mixed and reacted at 23 ° C. for 7 days to obtain a reaction product (AS-4). (2) 163.3 g of KBM902 and 172.2 g of diethyl maleate were mixed and reacted at 23 ° C. for 7 days to obtain a reaction product (AS-5). (3) 1,00 of urethane prepolymer (PUR-1)
0 g, reaction product (AS-4) 75 g, reaction product (AS-)
5) was put in a reaction vessel at a rate of 78 g, and under a nitrogen atmosphere
The mixture was reacted for 1 hour at 90 ° C. with stirring to obtain a liquid urethane resin (7). (4) A mixture (7) of a vinyl polymer and a urethane resin was obtained in the same manner as in (5) of Example 1 except that the urethane resin (7) was used instead of the urethane resin (1). It was (5) The above mixture (7) 1,000 g, Neo Polymer L-90 (trade name: Nippon Petrochemicals Co., Ltd., C ₉ hydrocarbon resin) was placed into a planetary mixer and 300g and NS400 at the rate of 500 g, reduced pressure After dehydration by heating at 100 ℃ below, cool to room temperature, 50g of KBM903, KBM
30 g and Stan No. 10 g of 918 was kneaded to obtain a urethane resin contact adhesive.

Comparative Example 1 1,000 g of a vinyl polymer / urethane resin mixture (1-1) and 500 g of NS400 were put in a planetary mixer and dehydrated by heating at 100 ° C. under reduced pressure and then at room temperature. Cool down to KBM9
No. 03, 30 g of KBM403 (trade name: γ-glycidoxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.) and Stan No. 10 g of 918 was kneaded to obtain a urethane resin contact adhesive.

Comparative Example 2 A silicone resin contact adhesive was obtained in the same manner as in Comparative Example 1 except that SAT200 was used instead of the vinyl polymer / urethane resin mixture (1-1). .

Comparative Example 3 A silicone resin contact adhesive was prepared in the same manner as in Comparative Example 1 except that ESGX-3406a was used instead of the vinyl polymer / urethane resin mixture (1-1). Obtained.

Comparative Example 4 A silicone resin contact adhesive was obtained in the same manner as in Comparative Example 1 except that MA440 was used instead of the vinyl polymer / urethane resin mixture (1-1). .

(Comparative Example 5) 700 g of SAT200, E
300 g of SGX-3406a and 500 of NS400
g in a planetary mixer at a rate of 100 g under reduced pressure
After dehydration by heating at 0 ° C, 50 g of KBM903, 30 g of KBM403 and Stan No. 918
Was kneaded to obtain a silicone resin contact adhesive.

The contact type adhesive obtained in each of the examples and comparative examples was used as a stainless steel material (SUS304 (2B);
2.5 cm x 10 cm) and apply it thinly
Under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, tack development time, tack range, and tack strength were examined in the following manner, and the results are shown in Tables 1 and 2.

Tack development time: time from application to tack development examined by finger touch Tack range: time until tack disappears after tack development: Tack strength: ○; Bond G10 (Konishi Co., Ltd., solvent-type chloroprene-based contact) Type adhesive) Strong tack △: Tack slightly weaker than bond G10 ×: Tack much weaker than bond G10 (no practical use)

Further, the contact type adhesives obtained in Examples and Comparative Examples were prepared by using two stainless steel materials (SUS304).
(2B); 2.5 cm × 10 cm) was applied and spread thinly, and a predetermined application time (open time) was taken under the conditions of a temperature of 23 ° C. and a relative humidity of 50%. After that, they were pasted together in an area of 2.5 cm × 2.5 cm, and pressed with an air cylinder press machine at a pressure of 0.98 MPa for 5 seconds, and then immediately subjected to tensile shear adhesive strength (JIS.
K 6850), and the strength (O.I.
T. The strength after 30 minutes) was examined in the following manner, and the results are shown in Tables 1 and 2.

Settling time: After applying both surfaces to an adherend and bonding them with an open time and immediately measuring the tensile shear adhesive strength, the adhesive strength is 0.1 N /
Pre-coating time to be ² mm ² or more Bondable time: Time from the appearance of shrinkage to the tensile shear adhesive strength of 0.1 N / mm ² or less immediately after the bonding, O. T. Strength after 30 minutes: Adhesive strength when an open time is taken for 30 minutes and the pieces are pasted and a tensile shear test is immediately performed.

[0079]

[Table 1]

[Table 2]

From the results shown in Tables 1 and 2, the urethane resin-based contact adhesive of the present invention is insufficient in the corresponding silicone resin-based contact adhesive or conventional silicone resin-based contact adhesive. It can be seen that, in addition to having the physical properties required for the agent, the tack range is long and the strength is maintained, the bonding time is long, and the strength after 30 minutes of open time is large. In particular, the combined use of a vinyl polymer as a component makes the above effects more remarkable. In addition, from the comparison between Example 1 and Comparative Example 1, by using the tackifying resin as a component of the adhesive, the tack range and the possible bonding time can be lengthened and the strength after 30 minutes of open time is improved. It is clear that you can.

[0081]

The urethane resin contact type adhesive of the present invention completely satisfies the physical properties required for the contact type adhesive, which cannot be satisfied by the conventional silicone resin type contact adhesive. be able to.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J040 BA202 DB032 DD052 DF012                       DF022 DF072 DG032 DL032                       DN032 EB032 EF131 EF281                       GA11 GA13 GA19 GA31 LA01                       MA06 MA12 NA12

Claims (2)

[Claims] 1. A urethane resin having a polyoxyalkylene polymer whose main chain contains at least polyoxyethylene and having groups represented by the following general formulas (1) and (2) in the molecule ( A urethane resin contact adhesive containing A) and a tackifying resin (B) as components. [Chemical 1] [Chemical 2] However, R ¹ is the following general formula (3), the following general formula (4), the following general formula (5) or a substituted or unsubstituted organic group having 1 to 20 carbon atoms, and R ² is 1 to 20 carbon atoms. Substituted or unsubstituted organic groups, X is a hydroxyl group or a hydrolyzable group,
n represents 0, 1 or 2, respectively, and when a plurality of R ^2's are present, the R ^2's may be the same or different, and when a plurality of R's are present, the X's may be the same or different. [Chemical 3] [Chemical 4] [Chemical 5] However, R ³ is a hydrogen atom or —COOR ¹⁰ , R ⁴ is a hydrogen atom or a methyl group, R ⁵ is —COOR ¹¹ or a nitrile group, and R ⁶ is a substituted or unsubstituted 2 to 1 to 20 carbon atom. the valent organic group, R ⁷ is also a good organic group optionally containing a molecular weight of 500 or less silicon atoms, R ⁸ and R ⁹ are the above-mentioned general formula (3) or the following general formula (6), respectively, R ⁸ and R ⁹ may be the same or different. R ¹⁰ and R ¹¹ each represent an organic group having a molecular weight of 500 or less. [Chemical 6] 2. A urethane resin containing the urethane resin (A) according to claim 1, a tackifying resin (B) and a vinyl polymer (C) obtained by polymerizing a polymerizable vinyl group-containing monomer as components. System contact adhesive.