JP2013032450A - Pressure-sensitive adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a pressure-sensitive adhesive composition that includes an oxyalkylene polymer having at least one silicon-containing group which has a hydroxyl or hydrolyzable group bonded to the silicon atom and can be crosslinked through the formation of a siloxane bond; a tackifier resin; and a curing catalyst, wherein the pressure-sensitive adhesive composition has less coloring and good releasability, good curability and good adhesive characteristics.SOLUTION: The pressure-sensitive adhesive composition includes, as essential components: (A) an oxyalkylene polymer having at least one silicon-containing group which has a hydroxyl or hydrolyzable group bonded to the silicon atom and can be crosslinked through the formation of a siloxane bond; (B) a tackifier resin other than a phenolic compound; and (C) a titanium compound.

Description

  The present invention comprises an oxyalkylene polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon-containing group that can be crosslinked by forming a siloxane bond, a tackifying resin, and a curing catalyst. The present invention relates to a pressure-sensitive adhesive composition that is low in color and has good release properties, curability and adhesive properties.

  To date, pressure-sensitive adhesive compositions obtained by blending a compound with a tackifier resin are well known. Among such compounds, a pressure-sensitive adhesive composition comprising a polyether containing a hydrolyzable silyl group and a tackifying resin can be applied with little or no organic solvent, and is therefore an environmental load. It has been proposed as a pressure-sensitive adhesive composition that does not wear (see, for example, Patent Document 1).

  A tin compound is used as a catalyst for curing the adhesive composition disclosed in the above patent document. Patent Document 2 discloses a pressure-sensitive adhesive composition comprising a polyether containing a hydrolyzable silyl group, a tackifier resin, and a zirconium compound. Patent Document 3 discloses a pressure-sensitive adhesive composition comprising a polyether containing a hydrolyzable silyl group, a tackifying resin, and a titanium compound.

Japanese Unexamined Patent Publication No. 55-056153 Japanese Patent Laid-Open No. 62-146959 WO2005 / 073333

  The pressure-sensitive adhesive composition of Patent Document 1 has a problem that the releasability from the silicone release paper is poor. That is, when pasted with a release paper or release film coated with a silicone release agent, or when coated and wound on a substrate coated with a silicone release agent as a back treatment agent, The peel resistance between the pressure-sensitive adhesive and the release paper or release film increases, and if it is bad, the release paper may be torn and become impossible to peel.

  As disclosed in Patent Document 2, when a zirconium compound is used as a curing catalyst, the releasability from the silicone release paper is improved. However, there is a problem that the curability of the pressure-sensitive adhesive composition is poor. As disclosed in Patent Document 3, when a titanium compound is used as a curing catalyst, both the releasability from the silicone release paper and the curability are improved. However, there is a problem that the pressure-sensitive adhesive composition is colored.

  The present invention has been made in view of the fact that there is no pressure-sensitive adhesive composition that is low in color and has good releasability, curability and adhesive properties with silicone release paper.

  As a result of various studies, the present inventor has (A) an oxyalkylene-based polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon-containing group that can be crosslinked by forming a siloxane bond. Copolymer (B) Tackifying resin that is not phenolic compound (C) Titanium compound is an essential component, so it can be applied with almost no solvent, good release from release paper, and good curing The present inventors have found that a low-colored pressure-sensitive adhesive composition having excellent properties and adhesive properties can be obtained, and have completed the present invention.

That is, this invention relates to the adhesive composition containing the following component (A), component (B), and component (C).
(A) Oxyalkylene polymer having at least one silicon-containing group that has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond (B) Tackifier that is not a phenolic compound Resin (C) Titanium compound The oxyalkylene polymer (A) has 0.6 to 1.5 hydrolyzable silyl groups in one molecule, a number average molecular weight of 15000 or more, and Mw / An oxyalkylene polymer having Mn ≦ 1.6 is preferred.
Examples of tackifier resins (B) include rosin resins, rosin ester resins, rosin ester derivatives, polymerized rosin resins, hydrogenated polymerized rosin resins, polymerized rosin ester resins, polymerized rosin ester derivatives, hydrogenated rosin resins, hydrogenated rosin ester resins. , Hydrogenated rosin ester derivative, terpene resin, hydrogenated terpene resin, petroleum resin (aliphatic, aromatic, alicyclic, copolymer, coumarone indene resin), hydrogenated petroleum resin, xylene resin, One or more selected from the group consisting of ketone resins, styrene resins, modified styrene resins, and epoxy resins are preferred.
As a titanium compound of (C), general formula (1):
Ti (OR ¹ ) ₄ (1)
Wherein R ¹ is an organic group, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and four R ^{1 s} may be the same or different from each other. Is preferred).
As a weight part number of tackifying resin (B), 20-100 weight part is preferable with respect to 100 weight part of oxyalkylene type polymers (A).

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a pressure-sensitive adhesive composition that is low in color and has good releasability, curability and adhesive properties with silicone release paper.

Examples of the main chain skeleton of the polyoxyalkylene polymer having a hydrolyzable silyl group in one molecule as the component (A) of the present invention include those having a repeating unit represented by the general formula (2).
General formula (2):
-R ² -O- ⁽²⁾
(Wherein R ² is a divalent alkylene group)
R ² in the general formula (2) is preferably a linear or branched alkylene group having 1 to 14, more preferably 2 to 4 carbon atoms. Specific examples of the repeating unit represented by the general formula (2) include —CH ₂ O—, —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O—, —CH ₂ CH (C ₂ H _{5 ) O -, - CH 2 C} (CH 3) 2 O -, - CH 2 CH 2 CH 2 CH 2 O- and the like. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, a polymer having —CH ₂ CH (CH ₃ ) O— as the main repeating unit is preferable from the viewpoint of availability and workability. The main chain of the polymer may contain a repeating unit other than the oxyalkylene group. In this case, the total of oxyalkylene units in the polymer is preferably 80% by weight or more, particularly 90% by weight or more.

  The structure of the polymer of the component (A) may be a linear polymer or a branched polymer, or a mixture thereof, but in order to obtain good release properties, the linear polymer is 50 It is preferable to contain it by weight% or more.

  The molecular weight of the component (A) polymer is preferably 15,000 to 100,000, more preferably 20,000 to 50,000 in terms of number average molecular weight. When the number average molecular weight is less than 15,000, the resulting pressure-sensitive adhesive composition becomes hard and good pressure-sensitive adhesive properties cannot be obtained. On the other hand, if the number average molecular weight exceeds 100,000, the viscosity becomes too high and the workability is remarkably lowered, which is not preferable. The number average molecular weight can be measured by various methods, but usually conversion from a terminal group analysis of a polyoxyalkylene polymer or measurement by a gel permeation chromatography (GPC) method is common. As the number average molecular weight of the present invention, those measured by a gel permeation chromatography (GPC) method in terms of polystyrene are used.

  The molecular weight distribution (Mw / Mn) of the polymer of component (A) is preferably 1.6 or less, more preferably 1.4 or less, because the polymer has a low viscosity.

  The hydrolyzable silyl group-containing organic polymer of the present invention can be obtained by introducing a hydrolyzable silyl group into a compound known as a polyether or polyol having a hydroxyl group at the terminal by an appropriate method.

  Such polymers have been proposed, for example, in JP-A-3-72527, JP-A-3-47825 and JP-A-3-79627.

  The polyether compound used in the present invention is a monoepoxide such as an alkylene oxide in an initiator such as a hydroxy compound having at least one hydroxyl group in the presence of a catalyst such as a metal porphyrin catalyst, a double metal cyanide complex catalyst, or a phosphazene catalyst. Can be made to react. Among these, a polyether produced using a double metal cyanide complex catalyst or a phosphazene catalyst is particularly preferred because a polyether having a low viscosity and no problem in hue can be obtained due to a narrow molecular weight distribution.

  The number of functional groups of the hydroxy compound used for the initiator is preferably 2 or more, and in addition to propylene glycol, glycerin, pentaerythritol, use of PPG, PPT (polyoxypropylene triol) and the like can be mentioned.

  Specific examples of the polyether include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyhexylene, polyoxytetramethylene and copolymers thereof.

  Particularly preferred polyethers include polyoxypropylene diol and polyoxypropylene triol, allyl-terminated polyoxypropylene, methallyl-terminated polyoxypropylene, and the like.

  As the silicon-containing functional group that can be crosslinked by forming the siloxane bond of the present invention, a generally known hydrolyzable silyl group can be used.

For example, a silyl group represented by the general formula (3) is preferable.
-SiX _a R ³ _3-a (3)
In the formula, R ³ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 8 or less carbon atoms, a phenyl group, or a fluoroalkyl group. Particularly preferred are methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, phenyl group and the like.

  X is a hydrolyzable group such as a halogen atom, an alkoxy group, an alkenyloxy group, an acyloxy group, an amide group, an amino group, an aminooxy group, a ketoximate group, an acid amide group, or a hydride group.

  Among these, the number of carbon atoms of the hydrolyzable group having a carbon atom is preferably 6 or less, and particularly preferably 4 or less. Preferred hydrolyzable groups include lower alkoxy groups having 4 or less carbon atoms, particularly methoxy groups, ethoxy groups, propoxy groups, propenyloxy groups and the like. a is 1, 2 or 3, and 2 or 3 is particularly preferable.

  The method for introducing the silicon group represented by the general formula (3) into the polyether is not particularly limited, but for example, it can be introduced by the following method.

(A) A method of reacting a polyether compound having a functional group with an olefin group introduced at the end thereof and a hydrosilyl compound represented by the general formula (4).
HSiX _a R ³ _3-a (4)
(Wherein R ³ , X and a are the same as above)

  Here, as a method of introducing an olefin group, a compound having a functional group capable of reacting with an unsaturated group and a hydroxyl group is reacted with a terminal hydroxyl group of the polyether compound, and an ether bond, an ester bond, a urethane bond, a carbonate bond, or the like. Examples thereof include a method of bonding, or a method of introducing an olefin group into a side chain by adding an olefin group-containing epoxy compound such as allyl glycidyl ether and copolymerizing when the alkylene oxide is polymerized.

(B) A method in which a compound represented by the general formula (5) is reacted at the end of a polyether compound having a functional group capable of reacting with an isocyanate compound.
(R ^3- ) _3-a SiX _a -R ⁴ NCO (5)
(In the formula, R ³ , X and a are the same as above. R ⁴ is a divalent hydrocarbon group having 1 to 17 carbon atoms.)

(C) After reacting a polyisocyanate compound such as tolylene diisocyanate to the end of a polyether compound having a functional group capable of reacting with an isocyanate compound to form an isocyanate group end, the isocyanate group is represented by the general formula (6). A method of reacting a W group of a silicon compound.
(R ^3- ) _3-a SiX _a -R ⁴ W (6)
(Wherein R ³ , R ⁴ , X and a are the same as above. W is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group and an amino group (primary or secondary).)

  (2) An olefin group is introduced at the end of a polyether compound having a functional group into which an olefin group can be introduced, and the olefin group and a mercapto group of the silicon compound represented by the general formula (6) in which W is a mercapto group How to react.

The polymer having a hydrolyzable silyl group which is the component (A) of the present invention preferably contains 0.6 to 1.5 hydrolyzable silyl groups in one molecule. When the hydrolyzable silyl group in one molecule of the component (A) is less than 0.6, a sufficient cured adhesive can not be obtained. On the other hand, when the number is 1.5 or more, the flexibility of the cured adhesive is impaired, and good adhesive properties cannot be obtained. The silyl group introduction rate (T ′ / T) of the present invention is determined using 1H-NMR (measured in a CDCl ₃ solvent using JNM-LA400 manufactured by JEOL Ltd.), and the methyl group of the polypropylene oxide main chain of the polymer. Relative value of peak integrated value of terminal allyl group —CH ₂ —CH═CH ₂ (near 5.1 ppm) with respect to peak integrated value (around 1.2 ppm) (T) and silyl-terminated polypropylene after hydrosilylation reaction Methylene group —CH ₂ —CH ₂ —CH ₂ —Si (OCH) bonded to the silicon atom of the terminal silyl group with respect to the peak integral value of the methyl group (around 1.2 ppm) of the polypropylene oxide main chain of oxide (A-2) ₃ ) Calculated from the relative value (referred to as T ′) of the peak integral value of ₃ (around 0.6 ppm).

  Since the phenolic compound causes coloring, the tackifying resin as the component (B) of the present invention is a tackifying resin other than the phenolic compound. For example, rosin resin, rosin ester resin, rosin ester derivative, polymerized rosin resin, hydrogenated polymerized rosin resin, polymerized rosin ester resin, polymerized rosin ester derivative, hydrogenated rosin resin, hydrogenated rosin ester resin, hydrogenated rosin ester derivative, Terpene resin, hydrogenated terpene resin, petroleum resin (aliphatic, aromatic, alicyclic, copolymer, coumarone indene resin), hydrogenated petroleum resin, xylene resin, ketone resin, styrene resin, modified Examples thereof include styrene resins, epoxy resins, and various modified products thereof. These may be used singly or in combination of two or more as required.

  The preferable compounding quantity of (B) component of this invention is 5-150 weight part with respect to 100 weight part of (A) component. More preferably, it is 10-120 weight part. The most preferred range is 20 to 100 parts by weight. If the amount is less than 5 parts by weight, the composition may be inferior in tackiness. If the amount exceeds 150 parts by weight, the polymer (A) has good affinity for various adherends, hydrophilicity, and chemical stability. Such characteristics may be impaired.

A conventionally well-known thing can be widely used for the titanium compound which is (C) component of this invention. Specifically, the general formula (1):
Ti (OR ¹ ) ₄ (1)
Wherein R ¹ is an organic group, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and four R ^{1 s} may be the same or different from each other. Among them, titanium alkoxide can be exemplified as a typical compound. In addition, as the compound represented by the general formula (1), a part or all of four OR ¹ groups in the general formula (1) are represented by the general formula (7):
-OCOR ⁵ (7)
(Wherein, R ⁵ is an organic group, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), and titanium acylate which is an acyloxy group represented by Other compounds represented by general formula (1) include general formula (8):

[Wherein R ⁶ and R ⁷ are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ and R ⁷ may be the same or different. 4-n R ⁶ may be the same as or different from each other, and n R ⁷ may be the same as or different from each other. A ¹ and A ² are selected from —R ^{8 and} —OR ⁸ (where R ⁸ is a hydrocarbon group having 1 to 20 carbon atoms). A ¹ and A ² may be the same or different. 4-n A ¹ may be the same or different from each other, and 4-n A ² may be the same or different from each other. n is 0, 1, 2, or 3. And / or the general formula (9):

(Wherein, R ⁶ , A ¹ , and A ² are the same as described above. R ⁹ is a divalent hydrocarbon group having 1 to 20 carbon atoms.)

Moreover, as a titanium compound not represented by the general formula (1), the general formula (10):
TiX ′ _4-a (OR ¹⁰ ) _a (10)
(In the formula, X ′ is a halogen atom, and 4-a X ′s may be the same or different from each other. R ¹⁰ is an organic group, more preferably 1 to 20 carbon atoms. A substituted or unsubstituted hydrocarbon group, and a R ^{10 s} may be the same or different from each other, and a is any one of 1, 2, and 3). And titanium alkoxide.

  Specific examples of the titanium alkoxide represented by the general formula (1) include titanium tetramethoxide, titanium tetraethoxide, titanium allyl oxide, titanium tetra n-propoxide, titanium tetraisopropoxide, titanium tetra n-butoxide. Titanium tetraisobutoxide, titanium tetra sec-butoxide, titanium tetra t-butoxide, titanium tetra n-pentyl oxide, titanium tetracyclopentyl oxide, titanium tetrahexyl oxide, titanium tetracyclohexyl oxide, titanium tetrabenzyl oxide, titanium tetraoctyl oxide, Titanium tetrakis (2-ethylhexyl oxide), titanium tetradecyl oxide, titanium tet Dodecyl oxide, titanium tetrastearyl oxide, titanium tetrabutoxide dimer, titanium tetrakis (8-hydroxyoctyl oxide), titanium diisopropoxide bis (2-ethyl-1,3-hexanediolato), titanium bis (2-ethylhexyloxy) ) Bis (2-ethyl-1,3-hexanediolato), titanium tetrakis (2-chloroethoxide), titanium tetrakis (2-bromoethoxide), titanium tetrakis (2-methoxyethoxide), titanium tetrakis (2 -Ethoxyethoxide), titanium butoxide trimethoxide, titanium dibutoxide dimethoxide, titanium butoxide triethoxide, titanium dibutoxide diethoxide, titanium butoxide tri Sopuropokishido, titanium dibutoxide diisopropoxide, titanium tetraphenoxide, titanium tetrakis (o-chloro phenoxide), titanium tetrakis (m-nitrophenoxide), titanium tetrakis (p- methyl phenoxide), and the like.

Specific examples of titanium acylate in which some or all of four OR ¹ groups in general formula (1) are groups represented by general formula (7) include titanium acrylate triisopropoxide and titanium methacrylate. Triisopropoxide, titanium dimethacrylate diisopropoxide, titanium isopropoxide trimethacrylate, titanium hexanoate triisopropoxide, titanium stearate triisopropoxide, and the like.

  Specific examples of the compound represented by the general formula (8) and / or the titanium chelate represented by the general formula (9) include titanium dimethoxide bis (ethylacetoacetate), titanium dimethoxide bis (acetylacetonate). , Titanium diethoxide bis (ethyl acetoacetate), titanium diethoxide bis (acetylacetonate), titanium diisopropoxide bis (ethyl acetoacetate), titanium diisopropoxide bis (methyl acetoacetate), titanium diisopropoxy Dobis (t-butylacetoacetate), titanium diisopropoxide bis (methyl-3-oxo-4,4-dimethylhexanoate), titanium diisopropoxide bis (ethyl-3-oxo-4,4, 4-trifluoropen Noate), titanium diisopropoxide bis (acetylacetonate), titanium diisopropoxide bis (2,2,6,6-tetramethyl-3,5-heptanedionate), titanium di-n-butoxide bis ( Ethyl acetoacetate), titanium di-n-butoxide bis (acetylacetonate), titanium diisobutoxide bis (ethylacetoacetate), titanium diisobutoxide bis (acetylacetonate), titanium di-t-butoxide bis (ethylacetate) Acetate), titanium di-t-butoxide bis (acetylacetonate), titanium di-2-ethylhexoxide bis (ethylacetoacetate), titanium di-2-ethylhexoxide bis (acetylacetonate), 1, 2-dioxy Tan titanium bis (ethyl acetoacetate), 1,3-dioxypropane titanium bis (ethyl acetoacetate), 2,4-dioxypentane titanium bis (ethyl acetoacetate), 2,4-dimethyl-2,4-di Examples thereof include oxypentane titanium bis (ethyl acetoacetate), titanium diisopropoxide bis (triethanolaminate), titanium tetrakis (ethyl acetoacetate), titanium tetrakis (acetylacetonate), and the like.

  Specific examples of the chelating reagent capable of forming the chelate ligand of the titanium chelate include β-diketones such as acetylacetone, β-ketoesters such as ethyl acetoacetate, and β-diesters such as ethyl malonate.

  When the titanium chelate is added as the component (C) of the present invention, the following method (e) or (f) can be used. (E) A method of adding a pre-chelated titanium compound. (F) A titanium compound capable of reacting with a chelating reagent such as titanium tetraisopropoxide or titanium diisopropoxide and a chelating reagent such as ethyl acetoacetate are added to the composition of the present invention. A method using a chelated titanium chelate.

  Specific examples of the halogenated titanium alkoxide of the general formula (10) include titanium chloride triisopropoxide, titanium dichloride diisopropoxide, titanium isopropoxide trichloride, titanium bromide triisopropoxide, titanium fluoride triiso Examples thereof include propoxide, titanium chloride triethoxide, and titanium chloride tributoxide.

  Specific examples of titanium compounds other than those described above include titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzene sulfonate) isopropoxide, dihydroxy titanium bis-lactate, and the like.

  Of these, titanium alkoxide is preferable from the viewpoint of coloring, and titanium chelate is preferable from the viewpoint of peel adhesion strength.

  The titanium compound of component (C) can be used in combination of two or more, in addition to being used alone.

  The amount of these titanium compounds used is 100 parts by weight of the organic polymer (A) and the tackifying resin (B) (100 parts of the organic polymer (A) depending on the kind of the tackifying resin (B)). 0.1 to 20 parts by weight is preferable, and 1 to 10 parts by weight is more preferable. If the amount of the titanium compound used is too small, the curing rate may be slow, and the curing reaction may not proceed sufficiently. On the other hand, if the amount of the titanium compound used is too large, local heat generation and foaming may occur during curing, and it may be difficult to obtain a good cured product.

  The method for preparing the pressure-sensitive adhesive composition of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, roll, kneader, etc. at room temperature or under heating, or a small amount of a suitable solvent is used. Ordinary methods such as dissolving and mixing the components can be used.

  Furthermore, the pressure-sensitive adhesive composition of the present invention can contain various known fillers and various additives.

In the curable composition of the present invention, in order to further increase the activity of the titanium compound, the following general formula (11):
R ³ _4-a Si (OR ³ ) _a (11)
(In formula, R < ³ >, a is the same as the above.) You may add the silicon compound shown. The silicon compound is not limited, but is directly connected to the Si atom in the general formula such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane and the like. It is preferable that at least one of R ³ is an aryl group having 6 to 20 carbon atoms because the effect of accelerating the curing reaction of the composition is great. In particular, diphenyldimethoxysilane and diphenyldiethoxysilane are particularly preferable because of low cost and easy availability. The compounding amount of the silicon compound is 100 parts by weight of the organic polymer (A) depending on the kind of the tackifier resin (B) with respect to 100 parts by weight of the total amount of the polymer (A) and the tackifier resin (B). On the other hand, it is preferably about 0.01 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight. When the compounding amount of the silicon compound is below this range, the effect of accelerating the curing reaction may be reduced. On the other hand, when the compounding amount of the silicon compound exceeds this range, the hardness and tensile strength of the cured product may decrease.

  To the composition of the present invention, a silane coupling agent, a reaction product of the silane coupling agent, or a compound other than the silane coupling agent can be added as an adhesion promoter. Specific examples of the silane coupling agent include isocyanate group-containing silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropylmethyldimethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- ( 2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ-ureido Amino group-containing silanes such as propyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane Epoxy group-containing silanes such as lan; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane, etc. Carboxysilanes; vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltriethoxysilane; γ-chloropropyltrimethoxy Examples include halogen-containing silanes such as silane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives of these, can also be used as silane coupling agents. . The silane coupling agent used in the present invention is usually based on 100 parts by weight of the total amount of the polymer (A) and the tackifier resin (B) (the organic polymer (A) depending on the kind of the tackifier resin (B)). Is used in the range of 0.1 to 20 parts by weight. In particular, it is preferably used in the range of 0.5 to 10 parts by weight.

  An antioxidant (antiaging agent) can be used in the composition of the present invention. When antioxidant is used, the heat resistance of hardened | cured material can be improved. Antioxidants include hindered phenols, monophenols, bisphenols, polyphenols, tinuvin 622LD, tinuvin 144; CHIMASSORB944LD, CHIMASSORB119FL (all manufactured by Ciba Geigy Japan); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68 (all are manufactured by Adeka Argus Chemical Co., Ltd.); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114 , Sanol LS-744 (all of which are manufactured by Sankyo Co., Ltd.). Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731. A hindered phenol type is preferable from the viewpoint of heat resistance, and a hindered amine light stabilizer is preferable from the viewpoint of coloring. The amount of the antioxidant used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts per 100 parts by weight of the organic polymer (A) having a reactive silicon group. Parts by weight.

  Various additives may be added to the composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, organic and inorganic fillers, UV absorbers, low and high molecular plasticizers, thixotropic agents, organic and inorganic pigments, flame retardants, curability modifiers, and radical inhibition. Agents, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, solvents, fungicides and the like. These various additives may be used alone or in combination of two or more.

  Next, a method for producing a pressure-sensitive adhesive product using the pressure-sensitive adhesive composition of the present invention will be described with reference to an example of a production process. However, in said manufacturing method, what is necessary is just to apply | coat an adhesive composition to a support body and to make it thermoset, and it is not limited to the following examples.

The pressure-sensitive adhesive composition of the present invention is applied onto a support with a coater, and this is heat-cured to obtain a pressure-sensitive adhesive product. As the support, films made of synthetic resin or modified natural products, paper, all kinds of cloth, metal foil, and the like can be used. Specific examples of the support include polyethylene, polypropylene, polyimide, polycarbonate, polyvinyl chloride, polyester, polyurethane, cellophane, impregnated paper, coated paper, fine paper, craft paper, cloth, acetate cloth, non-woven cloth, glass cloth, metal foil However, it is not necessarily limited to these. These may be used singly or may be used by laminating at least two kinds.
For the application, either a method of directly applying to a support or a method of applying to a release paper and curing and then transferring to a substrate can be used.

  In order to ensure the coatability to a support or a release paper, it is effective to add additives such as a repellency inhibitor and a releasability accelerator. As the repellency inhibitor and the releasability accelerator, silicone, acrylic, fluorine and the like can be used.

  In the case of the method of applying to a release paper, curing and transferring to a substrate, the release paper applied with a release agent such as silicone, olefin, or fluorine can be used. From the standpoint of securing, it is particularly preferable to use an olefin-based or solvent-free silicone-based release agent.

  The method of thermosetting is not particularly limited, but the temperature is preferably within the range of 50 ° C. to 180 ° C., although it varies depending on the type of polymer used and the compound to be added. The curing time varies depending on the polymer to be used, the compound to be added, the reaction temperature, and the like, but is usually in the range of 0.1 minute to 24 hours, preferably 1 minute to 10 hours, more preferably 1 minute to 1 hour. is there.

  The pressure-sensitive adhesive composition of the present invention can be used for various types of pressure-sensitive adhesive products for general office use, paper diapers, PP film bonding, re-peeling, general packaging, electricity, and fixing. Adhesive products using the adhesive composition of the present invention include packaging adhesive tapes, office adhesive tapes, coating masking tapes, electrical insulating adhesive tapes, binding adhesive tapes, protective adhesive tapes, and identification / decorative adhesives. Tapes and sheets, sports tapes, double-sided adhesive tapes, electromagnetic interference prevention films and tapes, re-peeling films and tapes, decorative board films, semiconductor chip transport tapes, marking films, protective films for deep drawing, glass scattering prevention films, foaming It can be used for adhesive tapes, waterproof / waterproof tapes, anticorrosive adhesive tapes, surface protective adhesive tapes, dicing adhesive tapes, backgrinding adhesive tapes, printing adhesive sheets, adhesive labels, and the like.

  In producing the above-mentioned adhesive product, chemicals, electromagnetic wave absorbing materials, light absorbers, foaming components, and the like can be added in accordance with these applications.

  Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the following examples.

(Production Example 1)
GPC measurement (polystyrene conversion) number average molecular weight 30000 by polymerizing propylene oxide using Actcol P-23 (manufactured by Mitsui Takeda Co., Ltd., polyoxypropylene glycol) as an initiator and zinc hexacyanocobaltate glyme complex. And then reacting allyl chloride with terminal hydroxyl groups, introducing unsaturated groups at all terminals, and further reacting 0.65 equivalents of methyldimethoxysilane with respect to the unsaturated groups. A compound (A-1) having 1.2 methyldimethoxysilyl groups was obtained. The viscosity (23 ° C .: B-type viscometer) of (A-1) was 46.8 Pa · s.
Examples 1-6 and Comparative Examples 1-8
The component shown in Table 1 was mix | blended in the ratio shown in Table 1, and about 60 weight part of toluene prepared the adhesive composition. The test method performed using the obtained adhesive composition is as follows.

(Color)
On the 50 μm polyester substrate (Lumirror film manufactured by Toray Industries, Inc., S105) so that the thickness after drying of the adhesive compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 8 is about 100 μm And dried and cured at 130 ° C. for 5 minutes and at 70 ° C. for 12 hours. Thereafter, a silicone release paper (manufactured by Fujimori Kogyo Co., Ltd., 80XT-032-No. 40) was bonded, and the color was observed. The results are shown in Table 1.

(180 ° peel strength)
The adhesive compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 8 were coated on a 50 μm polyester base material so that the thickness after drying was about 100 μm, and 70 ° C. for 5 minutes at 130 ° C. It was dried and cured at 12 ° C. for 12 hours. Thereafter, silicone release paper was bonded. The adhesive film thus obtained was bonded to a stainless steel plate (Nippon Tact Co., Ltd., SUS-304 (2B), 2 mm × 25 mm × 100 mm) polished with No. 280 polishing paper. After leaving this at room temperature for half a day, 180 ° peel strength was measured at a tensile rate of 300 mm / min in an atmosphere at 23 ° C. using an autograph manufactured by Shimadzu Corporation. The results are shown in Table 1.

(Curing speed)
The adhesive compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 8 were coated on a 50 μm polyester substrate so that the thickness after drying was about 100 μm, and heated in an atmosphere of 130 ° C. . The surface of the pressure-sensitive adhesive composition was lightly pressed with a micro spatula, and the time when the pressure-sensitive adhesive composition did not adhere to the tip of the spatula was measured. The results are shown in Table 1.

(Peelability)
The adhesive compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 8 were coated on a 50 μm polyester substrate so that the thickness after drying was about 100 μm, and a silicone release paper was bonded, It was dried and cured at 130 ° C. for 5 minutes. After leaving this at room temperature for half a day, 180 ° peel strength was measured at a tensile speed of 300 mm / min in an atmosphere of 23 ° C. using an autograph manufactured by Shimadzu Corporation. The results are shown in Table 1.

As shown in Table 1, when a zirconium compound was used as a curing catalyst (Comparative Examples 5 and 7), the cured product was colorless and had good releasability from the release paper and no adhesive residue, but cured. However, it took 10 minutes or more and the curability was poor. Moreover, when a tin compound was used as a curing catalyst (Comparative Examples 6 and 8), the cured product was colorless and cured in 3 minutes, but the release property from the release paper was poor and there was an adhesive residue.
When a titanium compound was used as a curing catalyst (Examples 1 to 6), the release property from the release paper was good and no adhesive remained, and practical curability and good adhesive properties were exhibited.
However, when a terpene phenol resin was used as the tackifier resin (Comparative Examples 1 to 4), the cured product was colored orange. In the case of using a hydrocarbon resin (Examples 1 to 3) or a rosin ester resin (Examples 4 to 6), coloring was suppressed.

Claims (9)

A pressure-sensitive adhesive composition containing the following component (A), component (B), and component (C).
(A) Oxyalkylene polymer having at least one silicon-containing group that has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond (B) Tackifier that is not a phenolic compound Resin (C) Titanium compound The pressure-sensitive adhesive composition according to claim 1, wherein the oxyalkylene polymer (A) is an oxyalkylene polymer having 0.6 to 1.5 hydrolyzable silyl groups in one molecule. The pressure-sensitive adhesive composition according to claim 1 or 2, wherein the oxyalkylene polymer (A) is an oxyalkylene polymer having a number average molecular weight of 15000 or more and 50000 or less and Mw / Mn ≦ 1.6. Tackifying resin (B) is rosin resin, rosin ester resin, rosin ester derivative, polymerized rosin resin, hydrogenated polymerized rosin resin, polymerized rosin ester resin, polymerized rosin ester derivative, hydrogenated rosin resin, hydrogenated rosin ester resin, water Hydrogenated rosin ester derivative, terpene resin, hydrogenated terpene resin, petroleum resin (aliphatic, aromatic, alicyclic, copolymer, coumarone indene resin), hydrogenated petroleum resin, xylene resin, ketone resin The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive composition is at least one selected from the group consisting of styrene resin, modified styrene resin, and epoxy resin. The pressure-sensitive adhesive according to any one of claims 1 to 4, wherein the number of parts by weight of the tackifier resin (B) is 20 to 100 parts by weight with respect to 100 parts by weight of the oxyalkylene polymer (A). Composition. The titanium compound (C) has the general formula (1):
Ti (OR ¹ ) ₄ (1)
Wherein R ¹ is an organic group, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and four R ^{1 s} may be the same or different from each other. 6. The pressure-sensitive adhesive composition according to any one of claims 1 to 5, wherein In the titanium compound (C), a part or all of the four OR ¹ groups in the general formula (1) are represented by the general formula (7):
-OCOR ⁵ (7)
(Wherein R ⁵ is an organic group, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), and is a titanium acylate which is an acyloxy group represented by The pressure-sensitive adhesive composition according to any one of claims 1 to 6. The titanium compound (C) has the general formula (8):

[Wherein R ⁶ and R ⁷ are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ and R ⁷ may be the same or different. 4-n R ⁶ may be the same as or different from each other, and n R ⁷ may be the same as or different from each other. A ¹ and A ² are selected from —R ^{8 and} —OR ⁸ (where R ⁸ is a hydrocarbon group having 1 to 20 carbon atoms). A ¹ and A ² may be the same or different. 4-n A ¹ may be the same or different from each other, and 4-n A ² may be the same or different from each other. n is 0, 1, 2, or 3. And / or the general formula (9):

(Wherein R ⁶ , A ¹ , and A ² are the same as described above. R ⁹ is a divalent hydrocarbon group having 1 to 20 carbon atoms.) The pressure-sensitive adhesive composition according to any one of claims 1 to 7. The titanium compound (C) has the general formula (10):
TiX ′ _4-a (OR ¹⁰ ) _a (10)
(In the formula, X ′ is a halogen atom, and 4-a X ′s may be the same or different from each other. R ¹⁰ is an organic group, more preferably 1 to 20 carbon atoms. A substituted or unsubstituted hydrocarbon group, and a R ^{10 s} may be the same or different from each other, and a is any one of 1, 2, and 3). The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive composition is a titanium alkoxide.