JP2003292928A - Urethane resin adhesive and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition hardly causing a blister, lifting and peeling even in a high-temperature and high-humidity condition, and having characteristics of keeping the optical function even in a high-temperature atmosphere, and to provide an adhesive and a method for producing the same. <P>SOLUTION: The adhesive contains the urethane resin composition synthesized from row materials comprising (e') a polyamino compound having a hydroxy group, (b) a polyisocyanate and (a) a polyol, having a bonded side represented by the formula (1): -R<SP>1</SP>-N(R<SP>3</SP>)-CO-NH-R<SP>2</SP>[wherein, R<SP>1</SP>is a divalent organic residue having an amino group derived from the polyamino compound (e'); R<SP>2</SP>is a polyvalent organic residue derived from the polyisocyanate (b); R<SP>3</SP>is a monovalent organic residue derived from the polyamino compound (e'), and containing at least one hydroxy group], and a urethane group. The concentration of the hydroxy group contained in the R<SP>3</SP>is 1×10<SP>-5</SP>-1×10<SP>-3</SP>mol/g. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a urethane resin composition suitable for an adhesive. In particular, the present invention relates to a pressure-sensitive adhesive suitable for adhesion of a polarizing plate that hardly causes deterioration of optical properties, a method for manufacturing the same, a pressure-sensitive adhesive sheet, and a laminate.

[0002]

2. Description of the Related Art A liquid crystal element exists between two substrates on which electrodes are arranged, and a polarizing plate or a laminated plate of a polarizing plate and a retardation plate is provided outside the two substrates. ing.

The optical film and its adhesive used in the liquid crystal display device are described in detail, for example, in JP-A-10-44291.

That is, in order to adhere this polarizing plate, high blister suppressing ability is required, and removability is also required due to its manufacturing process. In addition, practical characteristics such as light transmittance and phase difference (retardation value: product of refractive index of birefringence and film thickness) and other optical characteristics (optical function maintenance characteristics) and practical characteristics There is a demand for further enhancement of characteristics and high durability that can withstand more severe conditions.

At present, acrylic adhesives are almost exclusively used as adhesives for bonding optical films. These pressure-sensitive adhesives have been devised so as not to cause foaming or peeling in a heated and humidified atmosphere, but there are advantages and disadvantages.

In Japanese Patent Publication No. 7-98923, a weight average molecular weight (Mw) is obtained by copolymerizing an acrylic monomer and a macromonomer having a copolymerizable unsaturated double bond at one end.
It is described that this blister can be reduced by using 150,000 to 2 million graft polymers as an adhesive component. However, in this method, since the copolymerizability of the macromonomer is poor, some unreacted macromonomer remains, which adversely affects the physical properties and in terms of compatibility between the acrylic monomer and the macromonomer, There is a limit to the number of acrylic monomer species, macromonomer species, and their copolymerization parts, and turbidity may occur in the adhesive layer. Further, the macromonomer has a problem of high cost.

In Japanese Patent Laid-Open No. 11-12553, a specific styrene-based or α-methylstyrene-based tackifier is referred to as M
It describes a transparent pressure-sensitive adhesive film that has no problem in transparency and has cleared the above-mentioned blister problem by being added to an acrylic copolymer having w of 800,000 or more. But,
This tackifier has poor light resistance and heat resistance, and when left in the environment of ultraviolet rays or high temperatures for a long period of time, it has a problem of being colored brown and having a very poor appearance.

In JP-A-6-49425 and JP-A-8-3521, blister resistance is improved by adding a metal chelate-based agent and an aziridine-based crosslinking agent to an acrylic polymer having a specific monomer composition. It is stated that it can be expressed. However, when limited to these specific cross-linking agents, the cross-linking speed is relatively high as compared with the case where a commonly used isocyanate-based cross-linking agent is used, so that the anchoring property to the substrate is low and the formed tackiness is low. Since the layer has poor stress relaxation ability, there is a problem that floating or peeling occurs during long-term use, and the application range is limited.

In Japanese Patent Laid-Open Publication No. 10-44291, the functional group concentration is 5 × 1 on one side or both sides of the optical film material.
By using an acrylic polymer of / 10 ⁴ mol / g or less as the base polymer, it is possible to obtain a stable optical film which is excellent in both wet heat resistance and optical function maintaining characteristics, because the optical characteristics are not easily deteriorated for optical films. Is described. However, an optical film using an acrylic pressure-sensitive adhesive will lack the optical function maintaining property when the liquid crystal display device is further improved in performance and size.

[0010]

DISCLOSURE OF THE INVENTION The present invention provides a light transmittance and a phase difference (retardation value: birefringence) even in a high temperature atmosphere without causing blister, floating or peeling even under high temperature and high humidity conditions. (The product of refractive index and film thickness), a resin composition having a characteristic (optical function maintaining characteristic) that does not deteriorate optical characteristics, a method for producing the same, an adhesive sheet, a laminate using the same, and a polarizing plate An object is to provide a pressure-sensitive adhesive suitable for bonding optical films such as plates.

[0011]

Means for Solving the Problems As a result of repeated studies, the inventors of the present invention have a good blister resistance under high temperature and high humidity by containing a silyl group in a specific urethane resin,
The inventors have found that a urethane resin having excellent optical functional properties can be obtained, and completed the present invention.

As a result of repeated studies, the present inventors have found that the specific urethane resin has blister resistance and excellent optical functional characteristics, and completed the present invention.

Further, they have found that the blister resistance under high temperature and high humidity is further improved by containing a silyl group in the specific urethane resin, and completed the present invention.

[0014]

That is, the present invention is synthesized from a raw material containing a polyamino compound (e ') having a hydroxyl group, a polyisocyanate (b), and a polyol (a), and is represented by the following formula (1). It has a binding site and a urethane group shown, and the concentration of the hydroxyl group contained in R ³ is 1 ×.
The present invention relates to a pressure-sensitive adhesive containing a urethane resin composition having a concentration of 10 ⁻⁵ mol / g to 1 × 10 ⁻³ mol / g. .

Formula (1) —R ¹ —N (R ³ ) —CO—NH—R ² — (In the formula (1), R ¹ is derived from the polyamino compound (e ′) and has a divalent amino group. , R ² is a polyvalent organic residue derived from polyisocyanate (b), and R ³ is a monovalent organic residue containing at least one hydroxyl group derived from polyamino compound (e ′). .)

The present invention also relates to the above-mentioned pressure-sensitive adhesive, wherein the urethane resin composition contains an alkoxysilyl group.

The present invention also provides an adhesive comprising a urethane resin composition, the urethane resin composition 10
20 g / m ² of a mixture obtained by adding 1.5 parts by weight of hexamethylene diisocyanate trimethylolpropane adduct to 0 part by weight is coated on an optical film to form a urethane resin pressure-sensitive adhesive layer, and the optical film is the urethane resin. Adhesive layers are adhered to both sides of the glass plate so that the absorption axes are orthogonal to each other, and the glass plate is left in an autoclave at 50 ° C and 5 atm for 30 minutes.
When the glass plate to which the two optical films are adhered is heated for 00 hours and passed through a backlight through the glass plate to which the two optical films are adhered, there is substantially no decrease in polarization degree that affects visibility. Regarding an adhesive that can be given.

The present invention also relates to the above-mentioned pressure-sensitive adhesive, wherein the polyamino compound (e ') is a compound obtained by subjecting a polyamine (e) and a compound (f) having an unsaturated group to a Michael addition reaction.

The present invention also relates to the above-mentioned pressure-sensitive adhesive, wherein the polyamino compound (e ') is a compound (d) represented by the following formula (2). Formula (2)

[0020]

[Chemical 2]

(In the formula (2), Y represents a monovalent hydrocarbon group containing at least one functional group having active hydrogen, and may contain NH in the main chain. N is 0 or Represents 1, R
⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent hydrocarbon group containing no hydroxyl group, and R ⁶ and R 5
Each ⁷ independently represents a hydrogen atom or a monovalent hydrocarbon group. ) Further, the present invention relates to an adhesive comprising the above adhesive and a curing agent (D).

The present invention also relates to a laminate comprising a base material and the above-mentioned pressure-sensitive adhesive.

Further, the present invention is a method for producing a pressure-sensitive adhesive containing a urethane resin composition, wherein the urethane resin composition comprises a polyol (a) and a polyisocyanate (b) as a catalyst (c). The present invention relates to a method for producing a pressure-sensitive adhesive which is a urethane resin (C ') obtained by chain-extending a polyurethane prepolymer (A) with a polyamino compound (e') in the presence of the above.

Further, the present invention is a method for producing a pressure-sensitive adhesive containing a urethane resin, wherein the urethane resin comprises a polyol (a) and a polyisocyanate (b) in the presence of a catalyst (c). Polyurethane prepolymer (A) obtained by reacting with it is chain-extended with polyamino compound (e '), urethane resin having an isocyanato group at the terminal, and compound (h) having active hydrogen capable of reacting with the isocyanato group.
And a method for producing a pressure-sensitive adhesive which is a urethane resin (C ″) obtained by reacting

The present invention also relates to a method for producing the above-mentioned pressure-sensitive adhesive, wherein the compound (h) having active hydrogen capable of reacting with an isocyanato group contains a silane coupling agent (i) containing an alkoxysilyl group.

The present invention also relates to the method for producing the pressure-sensitive adhesive as described above, wherein the polyamino compound (e ') is a compound containing a hydroxyl group.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the urethane resin is
It has a binding site represented by the formula (1) and a urethane group.

The urethane group is formed mainly by reacting the polyol (a), which is a raw material of the urethane resin of the present invention, with an isocyanato group.

The binding site represented by the formula (1) is mainly formed by the reaction between the polyamine compound (e ') and the isocyanato group. (About Urethane Prepolymer (A)) The urethane prepolymer (A) used in the present invention is a polyol (a),
It is a compound having at least one isocyanato group at the terminal, which is obtained by reacting the polyisocyanate (b).
Further, as a raw material of the urethane prepolymer (A), if necessary, an amine described below, water, or a compound (j) having a group capable of reacting with an isocyanato group described below and an ionic group, or the like may be contained. (Regarding Polyol (a)) As the polyol (a), one or more high molecular weight polyols, bisphenols such as bisphenol A and bisphenol F, and alkylene oxides such as ethylene oxide and propylene oxide may be added to bisphenols. Glycols added, other polyols and the like can also be used. Furthermore, compounds having two or more active hydrogen groups obtained by reacting one or more of these with other compounds such as olefins and aromatic hydrocarbons can also be used.

The high molecular weight polyols are compounds having a repeating unit with a degree of polymerization of 2 or more and two hydroxyl groups, and examples thereof include polyester polyols, polyether polyols and polycarbonate polyols.

As the polyester polyols used in the present invention, known polyester polyols can be used.

As the polyester polyol, for example,
There is a polyester polyol in which a polyol component and a dibasic acid component are subjected to a condensation reaction. Among the polyols, diols include ethylene glycol, propylene glycol,
Dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3′-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol,
1,3-butanediol, 1,4-butanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, bisphenol A, and 3 or more Examples of the polyol having a hydroxyl group include glycerin, trimethylolpropane, pentaerythritol and the like, and dibasic acid components such as terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid and trimellitic acid. Group or aromatic dibasic acids or aromatic dibasic acids. In addition, ε-caprolactone poly (β-methyl-γ-
Valerolactone), polyvalerolactone, and other polyester lactones, polycarbonate polyols, silicon polyols and the like obtained by ring-opening polymerization of cyclic ester compounds such as lactones can be used.

The weight average molecular weight of the polyester polyols is preferably 500 to 5,000, more preferably 1,000 to 3,500.

As the polyether polyols used in the present invention, known polyether polyols can be used. For example, by condensation of tetrahydrofuran, or a polymer, copolymer or graft copolymer of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, or hexanediol, methylhexanediol, heptanediol, octanediol or a mixture thereof. It is possible to use polyether polyols, propoxylated or ethoxylated polyether polyols having two or more hydroxyl groups.

Further, as a polymerization initiator at the time of polymerizing alkylene oxide, for example, polypropylene glycol, ethylene glycol, glycerin, sorbitol, trimethylolpropane, trimethylolbutane,
Polyether polyols which are trivalent or higher alcohols such as trimethylolethane, 1,2,6-hexanetriol and pentaerythritol are also preferably used. Adducts of partially esterified polyhydric alcohols and polyether polyols can also be used. In this case, the polyether moiety may be a block polymer or a random polymer. Although the terminal to which the polyether polyol is added is a hydroxyl group, it may be partially an alkyloxy group or an aromatic hydrocarbonoxy group.

The weight average molecular weight of the polyether polyols is preferably 100 to 100,000, more preferably 500, so that the side chain effect can be easily obtained.
˜25,000, 1,000 to 10,000.

The polycarbonate polyol used in the present invention, a group represented by the following formula (3), Equation (3) - [- O- R 8 -O-CO-] m - ( wherein, R ⁸ is A divalent organic residue, m represents an integer of 1 or more), and a known polycarbonate polyol can be used.

Polycarbonate polyols are, for example,
1) Reaction of glycol or bisphenol with carbonic acid ester. 2) Obtained by the reaction of phosgene with glycol or bisphenol in the presence of alkali.

Specific examples of the carbonic acid ester used in the production method 1 include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate and propylene carbonate.

Specific examples of the glycol component or bisphenol used in the production method 1 include ethylene glycol, propylene glycol, dipropylene glycol,
Diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3 '
Dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9- Nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, 3,9-bis (1,1-dimethyl-2)
-Hydroxyethyl, 2,2,8,10-tetraoxospiro [5.5] undecane, bisphenols such as bisphenol A and bisphenol F, and bisphenols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to bisphenols. Kinds and the like can also be used. These compounds can be used alone or as a mixture of two or more.

The above glycol can also be used in the method of 2) in which phosgene is allowed to act on glycol or bisphenol in the presence of an alkali.

Specific examples of the polycarbonate polyol include Kuraray Polyol C series manufactured by Kuraray Co., Ltd.

Among them, PMHC-1050 and PMH
C-2050, C-1090, C-2090, C-10
65N, C-2065N, C-1015N, C-201
5N is preferable because it has flexibility and is excellent as a raw material for an adhesive.

The weight average molecular weight of the polycarbonate polyols is preferably 500 to 5,000, more preferably 1,000 to 3,500. If the weight average molecular weight is less than 500, the resin becomes too hard and becomes brittle when the urethane resin is synthesized. When the weight average molecular weight exceeds 5,000, the cohesive force of the urethane resin is insufficient.

The polyol (a) is the above polyether polyol and / or polyester polyol and / or
Alternatively, a urethane polyol having a hydroxyl group at the terminal may be obtained by reacting a polycarbonate polyol with less than the equimolar equivalent of the following polyisocyanate.

Other polyols include ethylene glycol, diethylene glycol, triethylene glycol, butanediol, propanediol, 1,6-
Two hydroxyl groups such as hexanediol, neopentyl glycol, cyclohexanedimethanol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl 2,2,8,10-tetraoxospiro [5.5] undecane And compounds having three or more hydroxyl groups such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, and methylglucoside.

(Regarding Polycarbodiimide (k)) The urethane resin pressure-sensitive adhesive of the present invention may contain polycarbodiimide (k) in order to improve the hydrolyzability of polyester.

Polycarbodiimide (k) used in the present invention
Is a group having a carbodiimide group (-N = C = N-), and a known polycarbodiimide can be used.

As the polycarbodiimide (k) used in the present invention, a high molecular weight polycarbodiimide produced by a decarboxylation condensation reaction of diisocyanate in the presence of a carbodiimidization catalyst can also be used. Examples of such a compound include those obtained by subjecting the following diisocyanates to a decarboxylation condensation reaction. 4,4'-diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,
4'-diphenylmethane diisocyanate, 4,4'-
Diphenyl ether diisocyanate, 3,3'-dimethyl-4,4'-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4
-Diisocyanate, isophorone diisocyanate,
4,4'-dicyclohexylmethane diisocyanate,
It is possible to use one of the tetramethylxylylene diisocyanates or a mixture thereof.

As the carbodiimidization catalyst, 1-phenyl-2-phosphorene-1-oxide, 3-methyl-2
-Phosphorene-1-oxide, 1-ethyl-3-methyl-2-phospholen-1-oxide, 1-ethyl-2-phospholen-1-oxide, or a phosphorene oxide such as a 3-phospholen isomer thereof is used. can do.

Examples of such a high molecular weight polycarbodiimide include the carbodilite series manufactured by Nisshinbo Industries, Inc. Among them, Carbodilite V-01, 03,
05, 07 and 09 are preferable because they have excellent compatibility with organic solvents.

Polycarbodiimide (k) in the present invention
Can be used in combination with a urethane resin, and can be used by incorporating a polycarbodiimide having an isocyanato group at the end into a urethane resin and can be used depending on the application. (About polyisocyanate (b)) As the polyisocyanate (b) used in the present invention, conventionally known ones can be used. For example, aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, Examples thereof include alicyclic polyisocyanate.

As the aromatic polyisocyanate, 1,
3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
2,4-Tolylene diisocyanate, 2,6-Tolylene diisocyanate, 4,4'-Toluidine diisocyanate, 2,4,6-Triisocyanate toluene, 1,
3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate and the like can be mentioned.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI),
Pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like can be mentioned.

As the araliphatic polyisocyanate,
ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate , 1,3-tetramethylxylylene diisocyanate and the like.

As the alicyclic polyisocyanate, 3-
Isocyanate Methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-Cyclopentane diisocyanate, 1,3-Cyclohexane diisocyanate, 1,4-Cyclohexane diisocyanate, Methyl-2,4-cyclohexane diisocyanate, Methyl-2 , 6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane and the like can be mentioned.

Further, a trimethylolpropane adduct of the above polyisocyanate, a trimer having an isocyanurate ring, or the like can be used in part. Polyphenylmethane polyisocyanate (PAPI), naphthylene diisocyanate, and modified products of these polyisocyanates may be used. As the modified polyisocyanate, a carbodiimide group, a uretdione group, a uretoimine group, a buret group reacted with water, an isocyanurate group, or a modified product having two or more kinds of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as the polyisocyanate (b).

The polyisocyanate (b) used in the present invention includes 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate),
From the viewpoint of weather resistance, it is preferable to use a non-yellowing type or hardly yellowing type polyisocyanate compound such as xylylene diisocyanate or 4,4′-methylenebis (cyclohexyl isocyanate) (hydrogenated MDI). (Catalyst (c)) When synthesizing the urethane prepolymer (A), a known catalyst (c) can be used. For example, tertiary amine compounds, organometallic compounds and the like can be mentioned.

Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (DBU) and the like.
Alternatively, they can be used together.

Examples of the organometallic compound include tin compounds and non-tin compounds.

Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide,
Dibutyltin dimaleate, dibutyltin dilaurate (D
BTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, 2-ethylhexanoic acid. Examples include tin.

Examples of the non-tin compound include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate and butoxy titanium trichloride, and lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate. , Iron such as iron 2-ethylhexanoate and iron acetylacetonate, cobalt such as cobalt benzoate and cobalt such as 2-ethylhexanoate, zinc such as zinc naphthenate and zinc 2-ethylhexanoate, zirconium naphthenate And so on.

Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

The above-mentioned catalysts such as tertiary amine compounds and organometallic compounds can be used alone depending on the case.
It is also possible to use the urethane prepolymer (A) in a stable and uniform manner by using dibutyltin dilaurate and tin 2-ethylhexanoate in combination, particularly when polyesterdiols and polyetherdiols are used in combination as the polyol component. Is obtained, which is preferable.

The organometallic compound catalyst used when synthesizing the urethane prepolymer (A) significantly accelerates the reaction when it further reacts with the amine described below. The reaction between the isocyanato group and the amino group is originally very fast, but in the presence of the organometallic compound catalyst, the reaction may be further promoted and may be difficult to control. At this time, if a chelate compound is present, it forms a chelate with the organometallic compound catalyst and adjusts the catalytic ability to facilitate control of the reaction with the amine.

Examples of the chelate compound include acetylacetone, dimethylglyoxime, oxine, dithizone,
Examples thereof include polyaminooxy acids such as ethylenediaminetetraacetic acid (EDTA), oxycarboxylic acids such as citric acid, condensed phosphoric acid and the like. Among the chelate compounds, acetylacetone is preferable because it is soluble in an organic solvent, has volatile properties, and can be easily removed if necessary.

The chelate compound remains in the polyurethane resin after the reaction. When using the polyurethane resin as an adhesive in the present invention, it is preferable to further add a curing agent, but at this time, the chelate compound also adjusts the reaction rate of the polyurethane resin and the curing agent, and as a result, An adhesive having excellent storage stability can be provided.

In the present invention, a known solvent is preferably used when synthesizing the urethane prepolymer (A). The use of a solvent serves to facilitate reaction control. As the solvent used for such a purpose, for example, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone,
Examples thereof include benzene, dioxane, acetonitrile, tetrahydrofuran, diglyme, dimethol sulfoxide, N-methylpyrrolidone and dimethylformamide. From the viewpoint of solubility of amine such as solubility of urethane resin and boiling point of solvent, ethyl acetate, toluene, methyl ethyl ketone or a mixed solvent thereof is particularly preferable. The concentration in the urethane prepolymer reaction system when a solvent is used is preferably 50 to 95% by weight of resin solids, more preferably 60 to
It is 90% by weight, and if the concentration is too low, the reactivity is lowered too much, which is not preferable.

(Regarding Polyamino Compound (e ′)) As the polyamino compound (e ′) described here, the compound (d) represented by the formula (2) and the compound having an unsaturated group with the polyamine (e) A compound obtained by subjecting (f) to a Michael addition reaction may be mentioned. The polyamino compound (e ′) preferably has a hydroxyl group so as to serve as a reaction point later.

The polyamino compound (e ') is used as a raw material for the urea-forming reaction for the purpose of modifying the urethane resin.

That is, the polyamino compound (e ') is
When the polyamine (e) has at least two primary or secondary amino groups, it is used to react with the urethane prepolymer (A) to form a urethane resin.

Furthermore, when the polyamino compound (e ') is obtained by Michael-adding the compound (f) having a quaternary ammonium salt group and an unsaturated group to the polyamine (e), it is possible to impart cationicity. Functions as a cationicity imparting agent. The polyamino compound (e ′) may or may not have a primary or secondary amino group. (Regarding Compound (d) Represented by Formula (2)) In the present invention, the compound (d) represented by formula (2) means the compound represented by formula (2)
Known compounds can be used as long as they are compounds defined by.

In the formula (2), Y represents a monovalent hydrocarbon group containing at least one functional group having active hydrogen, but may contain NH in the main chain. n represents 0 or 1, R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent hydrocarbon group containing no hydroxyl group, and R ⁶ and R ⁷ each independently represent a hydrogen atom. Alternatively, it represents a monovalent hydrocarbon group.

Here, examples of the monovalent hydrocarbon group containing no hydroxyl group include linear or branched alkyl groups,
Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and the like. Further, examples of the functional group having active hydrogen include a hydroxyl group, an amino group, a carboxyl group, and the like. Specific examples of the monovalent hydrocarbon group containing at least one functional group having active hydrogen include 3-aminopropyl. Group, a hydrocarbon group containing an amino group such as a (2-hydroxypropyl) aminomethylphenylmethyl group, or a hydrocarbon group containing a carboxyl group,
A hydrocarbon group containing a hydroxyl group may be mentioned.

As the compound (d), MXDA-PO1
(Manufactured by Mitsubishi Gas Chemical Company), MXDA-PO2 (manufactured by Mitsubishi Gas Chemical Company), MXDA-EO1 (manufactured by Mitsubishi Gas Chemical Company), M
XDA-EO2 (manufactured by Mitsubishi Gas Chemical Co., Inc.), 2-hydroxyethylaminopropylamine (manufactured by Koei Chemical Industry Co., Ltd.), aminoethylethanolamine, N- (2-hydroxyethyl) xylylenediamine (manufactured by Meisei Chemical Industry Co., Ltd.) ) And the like.

(Regarding Polyamine (e)) In the present invention, the polyamine (e) is a compound having at least two primary or secondary amino groups, and a compound (f) having at least one unsaturated group. It is used for synthesizing a Michael addition-reacted compound. Further, the polyamine (e) is used together with the polyol (a) and the polyisocyanate (b) to synthesize a urethane urea having at least one primary or secondary amino group at the terminal.

As the polyamine (e) used in the present invention, known ones can be used. Specifically, ethylenediamine, propylenediamine, trimethylenediamine,
Tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-
Aliphatic polyamines such as trimethylhexamethylenediamine, tolylenediamine, hydrazine, piperazine, isophoronediamine, dicyclohexylmethane-4,4 '
-Alicyclic polyamines such as diamines, and aromatic polyamines such as phenylenediamine and xylylenediamine.

Further, 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethylpropylene) diamine,
(Di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) diamine, (2-
Hydroxypropylethylene) diamine, (di-2-hydroxypropylethylene) diamine and other diamines having a hydroxyl group in the molecule, dimer diamine dicarboxylic acid is converted to an amino group, propoxyamine at both ends A polyoxyalkylene glycol diamine represented by the following formula (4) can also be used.

Formula (4) H ₂ N—CH ₂ —CH ₂ —CH ₂ —O ( _Cl H _2l —O) _k —CH ₂ —CH ₂ —CH ₂ —NH ₂ (wherein l in the formula (4) Is an arbitrary integer of 2 to 4, and k is an arbitrary integer of 2 to 50.)

Further, as the polyamine (e), a dendrimer having a primary or secondary amino group at the end can also be used. Such a dendrimer can be obtained by Michael-adding methyl acrylate to ammonia or ethylenediamine and further introducing a primary amino group at the terminal by ester amide exchange reaction as one step, and repeating the step if necessary. Examples of the star bust conjugates described in Japanese Patent Publication No. 6-70132, Japanese Patent Publication No. 7-2840, and Japanese Patent Publication No. 7-108860 are shown by the following structural formula (iv).
In addition, a reaction of reacting butylenediamine and acrylonitrile to reduce the terminal nitrile group to an amine is defined as one step, and represented by the following structural formulas (i), (ii), and (v) obtained by repeating the steps. , Tokuyodaira 8-5123
Examples thereof include propyleneimine-based dendrimers described in JP-B No. 45 and JP-A No. 9-508170. Further, there may be mentioned aromatic amide amine dendrimers represented by the following structural formula (iii), and star-shaped or comb-shaped branched aliphatic polyamino compounds disclosed in JP-A-7-00084. Furthermore, the polyamine obtained by the manufacturing method shown by Unexamined-Japanese-Patent No. 8-48770 or 8-92369 can be mentioned.

[0081]

[Chemical 3]

Structural formula (i) 4-Cascade: 1,4-Diaminobuta
ne [4]: propylamine

[0083]

[Chemical 4]

Structural formula (ii) 8-Cascade: 1,4-Diaminobutan
e [4] (1-azabutylidene) ⁴ propylamine

[0085]

[Chemical 5]

Structural formula (iii)

[0087]

[Chemical 6]

Structural formula (iv) 12-Cascade: ammonia [3] :( 1,4
-diaza-5-oxoheptylidene) ² : 3-aza-4-oxohexylamine

[0089]

[Chemical 7]

Structural formula (v) 12-Cascade: ammonia [3] :( 1-az
apropylidene) ² : ethylamine Among the above polyamines (e), isophorone diamine,
2,2,4-Trimethylhexamethylenediamine and hexamethylenediamine are preferable because the reaction can be easily controlled and hygiene is excellent. (Regarding Compound (f) Having Unsaturated Group) The compound (f) having an unsaturated group used in the present invention is used for the purpose of modifying the urethane resin. Therefore, the kind of the compound (f) having an unsaturated group to be used can be arbitrarily selected according to the purpose of modification.

Examples of the structural formula of R ^{3 in} the above formula (1) include the following formulas (5) to (15).

[0092]

[Chemical 8]

In the formulas (5) to (15), Y ^{1 to} Y ¹¹ are each independently a hydrogen atom or a weight average molecular weight of 15 to 2
It is a monovalent organic residue of 0,000, preferably 20 to 10,000.
Y ¹¹ is a direct bond or a divalent organic residue. Also, X
Represents a hydrogen atom or an alkyl group such as a methyl group.

In the present invention, as the organic residue, an alkyl group, a polyalkylene glycol group, an alkoxy group,
Examples thereof include a phenoxy group, a hydroxyl group, a carboxyl group, a perfluoroalkyl group, an alkoxysilyl group, an epoxy group, an amide group, a dialkylamino group, and a nitrogen-containing group such as a quaternary ammonium salt group.

As the unsaturated compound having the above structural formula, for example, the formula (5) is a (meth) acrylic unsaturated compound,
Formula (6) is an amide unsaturated compound, Formula (7) is a fatty acid vinyl unsaturated compound, Formula (8) is a vinyl ether unsaturated compound, Formula (9) is an α-olefin unsaturated compound, Formula (10) Is an allyl unsaturated compound, Formula (11) is an allyl acetate unsaturated compound, Formula (12) is a vinyl cyanide unsaturated compound, Formula (13) is a styrene or vinylbenzene unsaturated compound, Formula (14) Is an alicyclic olefinically unsaturated compound, and formula (15) is a part of the compound (d) represented by formula (2).

The kind of the compound (f) having an unsaturated group to be used can be arbitrarily selected according to the purpose of modification, but the compound (f) having an unsaturated group is selected by paying attention to the functional group of the compound (f) having an unsaturated group. Preferably. Examples of the functional group contained in the compound (f) having an unsaturated group include an alkyl group, a polyalkylene glycol group, an alkoxy group, a phenoxy group, a hydroxyl group, a carboxyl group, a perfluoroalkyl group, an alkoxysilyl group, an epoxy group, Furthermore, examples include an amide group, a dialkylamino group, a nitrogen-containing group such as a quaternary ammonium salt group, and the like.

Examples of the amide-based unsaturated compound of the formula (6) include (meth) acrylamide and N-methylol (meth).
Acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide,
Monoalkylol (meth) acrylamides such as N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl (meth) ) Acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-
Methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N
-Propoxymethylmethacrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide,
N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide, N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) meth Examples include dialkyrol (meth) acrylamide such as acrylamide.

Examples of the fatty acid vinyl-based alkyl group-containing unsaturated compound of the formula (7) are vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate. Etc. can be illustrated.

Further, examples of the vinyl ether-based unsaturated compound containing an alkyl group of the formula (8) include butyl vinyl ether and ethyl vinyl ether.

Further, as the α-olefin type alkyl group-containing unsaturated compound of the formula (9), 1-hexene, 1
-Octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadece, and other unsaturated compounds, as vinyl compounds, allyl compounds such as allyl acetate, allylbenzene and allyl cyanide, vinyl cyanide, vinyl Examples thereof include vinyl compounds such as cyclohexane, vinyl methyl ketone, styrene, α-methyl styrene, 2-methyl styrene, and chlorostyrene.

Examples of the ethynyl compound include acetylene, ethynylbenzene and ethynyltoluene.

Hereinafter, the (meth) acrylic unsaturated compound of the formula (5) will be exemplified.

Examples of the (meth) acrylic alkyl group-containing unsaturated compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth)
Acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate,
Undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth)
Carbon number 1 such as acrylate, nonadecyl (meth) acrylate, icosyl (meth) acrylate, henicosyl (meth) acrylate, docosyl (meth) acrylate
Alkyl group-containing acrylate or corresponding methacrylate having an alkyl group having 2 to 10 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably having 2 to 8 carbon atoms, for the purpose of adjusting the polarity. Is mentioned. When the purpose is to adjust the leveling property and the like, the number of carbon atoms is preferably 6 or more. If the number of carbon atoms is 23 or more, the Michael addition reaction is difficult to proceed, depending on the purpose.

As the polyalkylene glycol group-containing unsaturated compound, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, polyethylene glycol. Examples include mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth), and the like.

Further, the unsaturated compound containing a polyalkylene glycol group and having an alkoxy group at the terminal is methoxyethylene glycol (meth).
Acrylate, methoxydiethylene glycol (meth)
Acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meth) acrylate, n-pentaxytetraethylene glycol (meth) acrylate,
Tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol (meth) Acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) Acrylate,
Examples thereof include ethoxy polyethylene glycol (meth) acrylate.

Further, as the unsaturated compound containing a polyalkylene glycol group and having a phenoxy group at the terminal, phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) Examples thereof include acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and phenoxytetrapropylene glycol (meth) acrylate.

As the hydroxyl group-containing unsaturated compound other than the above, 2-hydroxyethyl (meth) acrylate, 2-
Examples thereof include hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, and allyl alcohol.

Examples of the unsaturated compound containing a carboxyl group include maleic acid, fumaric acid, itaconic acid, citraconic acid, or their alkyl or alkenyl monoesters, phthalic acid β- (meth) acryloxyethyl monoester, and isophthalic acid β-. (Meth) acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, etc. You can do it.

Examples of the dialkylamino group-containing unsaturated compound include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate methylethylaminoethyl (meth) acrylate, dimethylaminostyrene and diethylaminostyrene.

Further, the unsaturated compound containing a dialkylamino group is obtained by quaternary ammoniumation, and as a counter ion, a halogen ion such as Cl-, Br-, I- or QSO3- (Q: 1 to 12 carbon atoms is used. As the quaternary ammonium salt group-containing unsaturated compound having an alkyl group),
(Meth) acrylic acid dimethylaminoethyl methyl chloride salt, trimethyl-3- (1- (meth) acrylamide-1,1-dimethylpropyl) ammonium chloride, trimethyl-3- (1- (meth) acrylamidopropyl) ammonium chloride, and Trimethyl-3-
(1- (meth) acrylamide-1,1-dimethylethyl) ammonium chloride and the like can be mentioned.

As the perfluoroalkyl group-containing unsaturated compound, perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl ( (Meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, per Carbon such as fluoropropylpropyl (meth) acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctylamyl (meth) acrylate, perfluorooctylundecyl (meth) acrylate Perfluoroalkyl (meth) acrylates having 1 to 20 perfluoroalkyl groups; perfluoroalkyl such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene, and perfluoro such as alkylenes An alkyl group-containing unsaturated compound can be exemplified.

Examples of unsaturated compounds having an alkoxysilyl group include vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane and derivatives thereof. it can.

Furthermore, glycidyl acrylate, 3,4-
Examples thereof include epoxy group-containing unsaturated compounds such as epoxycyclohexyl acrylate.

Further, in the case of imparting curability to the Michael addition type urethane resin by active energy, the compound (f) having an unsaturated group having two or more unsaturated groups is used.
Can be used. Two or more as an unsaturated group
(Meth) acryloyl group or 1 acryloyl group and 1
The compound (f) having an unsaturated group having at least one methacryloyl group is preferably used.

More specifically, or as the compound (f) having an unsaturated group having one acryloyl group and one or more methacryloyl groups, 2-hydroxy-3-acryloxypropyl methacrylate, Examples of the compound (f) having an unsaturated group having one or more (meth) acryloyl groups include ethylene glycol di (meth)
Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
Polypropylene glycol di (meth) acrylate,
1,3 butanediol di (meth) acrylate, 1,4
Butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) acrylate, diethylene di (meth) acrylate, polyethylene Glycol di (meth) acrylate, trisacryloyloxyethyl isocyanurate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, epoxy adipic acid (meth) acrylate, hydrogenated bisphenol ethylene oxide di (meth) acrylate , Ethylene glycol glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate Relate, ethylene oxide adduct trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Pentaerythritol tetra (meth) acrylate, ethylene glycolated pentaerythritol tri (meth) acrylate
Acrylate, propylene glycolated pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolethane (meth) acrylate, tetramethylolmethane tri (meth) acrylate, dipentaerythritol alkylate (meth) acrylate, Actilane 421
(AKCROS CHEMICAL), Actilan
Examples thereof include those having 2 or more functional groups such as e423 (AKCROSCHEMICAL). These may be used alone or in combination of two or more.

The above-mentioned compound (f) having an unsaturated group can be used alone or in combination of two or more kinds.

The Michael addition reaction between the polyamine (e) and the compound (f) having an unsaturated group is carried out by the polyamine (e)
1 molar equivalent of active hydrogen of the amino group of 1 reacts with 1 molar equivalent of the unsaturated group of the compound (f) having an unsaturated group. Since the polyamine (e) easily Michael-adds to the vinyl group or ethynyl group of the compound (f) having an unsaturated group having an electron-withdrawing group, the (meth) acrylic compound, especially the acrylate compound is unsaturated. Group-containing compound (f)
Is preferred as Further, when comparing the acrylate-based compound and the corresponding methacrylate-based compound, the acrylate-based compound is preferable because the efficiency of the Michael addition reaction is good.

As a method for synthesizing the polyamino compound (e '), a known method relating to the Michael addition reaction can be used as it is. When the unsaturated compound is a (meth) acrylic compound, especially an acrylate compound, the reaction proceeds at 10 to 100 ° C. under a catalyst such as alcohol, if necessary. Depending on the type of unsaturated compound used, a reaction temperature of 40 to 80 ° C is preferable. If the reaction temperature is too high, an ester amide exchange reaction occurs, which is not preferable. Further, when the unsaturated compound does not have an electron-withdrawing group, the reaction becomes possible in the presence of a metal catalyst, and in this case, when the reaction is carried out at 60 to 100 ° C while heating in the presence of the catalyst, an appropriate reaction rate is obtained. Very preferable. Further, the synthetic solvent may or may not be used, and its type is not particularly limited,
Known solvents such as methyl ethyl ketone, toluene, acetone and benzene can be used. When the compound (f) or polyamine (e) having an unsaturated group to be used does not contain a hydroxyl group, an alcohol solvent such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol or n-butyl alcohol, or It is preferable to use a mixed solvent thereof. When a reaction solvent is used, the solution concentration is preferably 20% or more, more preferably 50% or more. If the concentration is less than this, the reaction is difficult to proceed, which is not preferable. The reaction time varies depending on the type of unsaturated compound used, but is 30
Finish in minutes to 5 hours.

The ratio of the polyamine (e) to the compound (f) having an unsaturated group is such that at least two secondary or primary amino groups remain in the polyamino compound (e ') obtained by the reaction. When it is carried out, it is not particularly limited, but is preferably 0.1 to 1.0 mol, and more preferably 0.2, relative to 1 mol of the primary amino group contained in the polyamine (e).
It is preferable to react at a ratio of about 0.98 mol. If it is less than this, the effect of the side chain is less likely to appear.

The urethane resin (C ') is a polyamino compound (e) obtained by Michael-adding the urethane prepolymer (A) having an isocyanato group at the terminal and the polyamine (e) and the compound (f) having an unsaturated group. ') And, if necessary, polyamine (e), and further, if necessary, compound (h) having active hydrogen capable of reacting with an isocyanato group to give a urethane resin (C "). be able to.

The active hydrogen capable of reacting with an isocyanato group is a hydrogen atom of a hydroxyl group or an amino group, and the compound (h) having active hydrogen capable of reacting with an isocyanato group is a functional group capable of reacting with an isocyanato group. Examples of the compound include a monoamine compound and the like, which reacts with the unreacted residual isocyanate group at the end of the urethane resin (C ′) to stabilize the reaction activity of the resin. Compound (h)
Will be described later.

(Regarding Alkoxysilyl Group and Silane Coupling Agent (i)) In the present invention, the urethane resin composition preferably has an alkoxysilyl group in order to improve the adhesiveness of the urethane resin adhesive.

The alkoxysilyl group is usually a functional group in which an alkoxy group and a silicon atom are directly bonded, and includes a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group. In terms of, a trialkoxysilyl group is used. The compound having an alkoxysilyl group is a so-called alkoxysilane, and particularly when it further has another functional group, it is referred to as a silane coupling agent (i).

To introduce an alkoxysilyl group into the urethane resin composition, 1. Alkoxysilane or silane coupling agent (i) is mixed with urethane resin. 2. An alkoxysilyl group is chemically introduced into the urethane resin by using the silane coupling agent (i) in the urethane resin. There is a method such as.

As an example of the latter, for example, a urethane resin having an isocyanato group is reacted with a silane coupling agent (i) having a functional group capable of reacting with an isocyanato group (for example, an amino group).

As the silane coupling agent (i), a known silane coupling agent can be used.

For example, vinyl-based silane coupling agent,
Amino silane coupling agents, epoxy silane coupling agents, chloro silane coupling agents, methacryloxy silane coupling agents, mercapto silane coupling agents, cationic silane coupling agents, isocyanate silane coupling agents, etc. Can be mentioned.

As the vinyl-based silane coupling agent,
Examples thereof include vinyltrimethoxysilane and vinyltriethoxysilane.

As the amino silane coupling agent,
Examples thereof include N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

The amino silane coupling agent can be introduced as a compound (h) into the urethane resin by reacting it with a urethane resin composition having an isocyanato group at the terminal.

Epoxy silane coupling agents include 3-glycidoxypropyltrimethoxysilane and 3
-Glycidoxypropylmethyldimethoxysilane, 2-
Examples include (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

As the chloro-based silane coupling agent,
Examples thereof include 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-chloropropyltrimethoxysilane and the like.

Examples of the methacryloxy silane coupling agent include 3-methacryloxypropyltrimethoxysilane.

Examples of the mercapto-based silane coupling agent include 3-mercaptopropyltrimethoxylane.

As the cationic silane coupling agent, N- [2- (vinylbenzylamino) ethyl] -3-
Examples include aminopyropyrtrimethoxysilane and hydrochloride.

Examples of the isocyanate type silane coupling agent include γ-isocyanatopropyltriethoxysilane.

Further, the isocyanate type silane coupling agent can be introduced into the urethane resin by reacting with the urethane resin having active hydrogen capable of reacting with the isocyanato group.

The silane coupling agent (i) used in the present invention is 0.1% based on 100 parts by weight of the urethane resin.
It is preferably contained in an amount of 01 to 10 parts by weight.
More preferably, it is contained in an amount of 0.05 to 5 parts by weight. When the content of the silane coupling agent (i) exceeds 10 parts by weight, the initial adhesive force is too low and peeling occurs. If the amount is less than 0.01 part by weight, the effect of the silane coupling agent (i) does not appear, and when used in a large-sized optical film device, the alkoxysilane that is floated under high temperature and high humidity conditions is a known alkoxysilane. Xylan can be used. For example, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, tetramethoxysilane, methyltriethoxysilane, tetraethoxysilane, methyldimethoxysilane, methyldiethoxysilane, dimethylethoxysilane, Dimethylvinylmethoxysilane, dimethylvinylethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, n-hexyldiethoxysilane, n-decyl Trimethoxysilane etc. are mentioned.

When used in a large-sized optical film device, the alkoxysilane used in the present invention is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the urethane resin. preferable. More preferably, it is contained in an amount of 0.05 to 5 parts by weight. If the content of alkoxyxylan exceeds 10 parts by weight, the initial adhesive strength is too low and peeling occurs. If the amount is less than 0.01 part by weight, the effect of alkoxyxylan does not appear, and floating may occur under high temperature and high humidity conditions.

(Regarding Manufacturing Process) The urethanization reaction for producing the urethane prepolymer (A) in the present invention can be carried out by various methods, but is roughly classified into the following two methods. 1) Polyol (a), polyisocyanate (b), and optionally a compound (j) having a group capable of reacting with an isocyanato group and an ionic group, and / or a solvent, and / or a catalyst (c) A method of charging the entire solution. 2) a polyol (a), and optionally a compound (j) having a group capable of reacting with an isocyanato group and an ionic group,
And / or a solvent is charged into a flask, the polyisocyanate (b) is added dropwise, and then the catalyst (c) is added if necessary. When the reaction is precisely controlled, 2) is preferable. The reaction temperature for obtaining the urethane prepolymer (A) is 1
20 ° C or lower is preferable. More preferably 50-110 ° C
Is. When the temperature is higher than 110 ° C, it becomes difficult to control the reaction rate, and it becomes impossible to obtain a urethane prepolymer having a predetermined weight average and structure. The urethanization reaction is preferably carried out in the presence of a catalyst at 50 to 110 ° C. for 1 to 20 hours.

Examples of the compound (j) include anionic functional group-containing polyols.

As the anionic functional group-containing polyol, for example, a polyol having a carboxyl group, a sulfone group or the like can be used, but it is particularly preferable to use a carboxyl group-containing polyol. As the carboxyl group-containing polyol, dimethylolpropionic acid, 2,2-dimethylolacetic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, dimethylolalkanoic acid such as dihydroxypropionic acid, dihydroxysuccinic acid, dihydroxy Examples include benzoic acid. Particularly, dimethylolpropionic acid and 2,2-dimethylolbutyric acid are preferable from the viewpoint of reactivity and solubility. These can be used alone or in combination.

The compounding ratio of the polyol (a) and the polyisocyanate (b) greatly depends on the reactivity of the compound, the abundance ratio of the compound having 3 or more valences, and the intended use of the obtained resin. In order for the urethane prepolymer to have at least one isocyanato group, 1 mol of the functional group capable of reacting with the isocyanato group of the polyol (a) and the compound (j) should have an isocyanato group of the polyisocyanate (b). It is necessary to be more than 1 mol, preferably 1.01 to 4.00 mol, more preferably 1.40.
A suitable range is 3.00 mol.

The urethane prepolymer (A) further comprises
The urethane resin having a urethane urea bond is chain-extended with the polyamino compound (e ′).

In the present invention, the isocyanato group contained in the urethane prepolymer (A) which is an isocyanato group-containing compound or polyisocyanate, and the polyamino compound (e ′) or the compound (h) having active hydrogen capable of reacting with the isocyanato group are The urea formation reaction with the primary or secondary amino group possessed is roughly classified into the following two methods. 1) A method in which a solution containing an isocyanato group-containing compound is placed in a flask and a solution containing an amino group-containing compound is added dropwise. 2) A method of charging a solution containing an amino group-containing compound into a flask and dropping a solution of a compound having an isocyanato group.

The synthesis is carried out in such a way that the reaction becomes stable, but if there is no problem in the reaction, the method 1) which is easy to operate is preferable. In the present invention, the temperature of the urea reaction is preferably 100 ° C or lower. More preferably, it is 70 ° C. or lower. 70 ° C
However, if the reaction rate is high and cannot be controlled, 50 ° C or lower is more preferable. When the temperature is higher than 100 ° C., it is difficult to control the reaction rate, and it is difficult to obtain a urethane resin having a predetermined molecular weight and structure. The temperature in the reaction system is preferably set to 50 ° C or lower, more preferably 40 ° C or lower.

The compounding ratio of the urethane prepolymer (A) and the amino group-containing compound is not particularly limited and may be arbitrarily selected depending on the application and the required performance. Usually, 1 mol of the isocyanato group in the isocyanato group-containing compound is used. With respect to the number of moles of the functional group of the amino group in the amino group-containing compound, preferably 0.70 to 0.97 in the case of an isocyanato group excess system,
It is more preferably 0.8 to 0.96, preferably 1.001 to 1.40, and more preferably 1.01 to 1.2 in an amino group excess system. If it is out of this range, the molecular weight does not become a predetermined value, which is not preferable.

The resin composition having a urethane urea bond has a partial structural formula represented by the formula (1). In the formula (1), R ¹ is a divalent organic residue having an amino group derived from the polyamino compound (e ′), R ² is a polyvalent organic residue derived from the polyisocyanate (b), and R ³ is , Represents an organic residue containing a monovalent oxygen atom derived from the polyamino compound (e ′).

The urethane resin pressure-sensitive adhesive of the present invention has a hydroxyl group concentration contained in R ³ of 1 × 10 ⁻⁵ mol / g to 1 × 10 ⁻³ mol / g.
Limited to g. The concentration of hydroxyl group contained in R ³ is 1 × 10 ^-5
If it is less than mol / g, the cohesive force will be insufficient and it will not function as an adhesive for optical films. The concentration of hydroxyl group contained in R ³ is g to 1
When it exceeds 10 ⁻³ mol / g, the cohesive force of the resin becomes too high and the adhesiveness is lost. The concentration of the hydroxyl group contained in R ³ here was calculated as follows.

Calculation Method of Hydroxyl Concentration Contained in R ^{3 The} number of moles of the hydroxyl group added is calculated from the amount of the hydroxyl group-containing acrylic monomer or hydroxyl group-containing amine used in the synthesis.
This value is divided by the total amount of the resin component to calculate the hydroxyl group concentration contained in R ³ .

(Regarding Compound (h)) The urethane resin having an isocyanato group at the terminal can be further reacted with a compound (h) having an active hydrogen capable of reacting with an isocyanato group, if necessary.

The compound (h) having active hydrogen capable of reacting with the isocyanato group plays a role of controlling the molecular weight and reacting with the unreacted isocyanato group remaining at the end of the urethane resin to stabilize the reaction activity of the resin. .

The compound (h) having an active hydrogen capable of reacting with an isocyanato group used in the present invention is, for example, diethylamine, di-n-butylamine or di-n-, in addition to the above-mentioned silane coupling agent (i). In addition to dialkylamines such as octylamine, dicyclohexylamine and diisononylamine, monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tri (hydroxymethyl) aminomethane, 2-amino-2-ethyl- Monoamines having a hydroxyl group such as 1,3-propanediol, monomethylhydrazine, 1,1-
Alkylhydrazines such as dimethylhydrazine and benzylhydrazine, formhydrazide, acetohydrazide,
Monoamine compounds having a tertiary amino group and a primary amino group on one side, such as hydrazides such as lauric acid hydrazide, N, N-dimethyl-1,3-propanediamine, N, N diethyl 1,3-propanediamine, etc. Among the compounds (h) having active hydrogen capable of reacting with the isocyanato group, a monoamine having a hydroxyl group such as 2-amino-2-methyl-propanol is a urethane resin having a hydroxyl group at the terminal and excellent in storage stability. You can get it. Furthermore, a urethane resin having a hydroxyl group at the terminal is preferable because the hydroxyl group at the terminal also functions as a crosslinking site when a polyisocyanate-based curing agent is added to crosslink. In the case of a monoamine having a hydroxyl group, both the amino group and the hydroxyl group can react with the terminal isocyanato group of the urethane resin, but the reactivity of the amino group is higher and it preferentially reacts with the isocyanato group.

In addition, monoamine compounds having a tertiary amino group and a primary amino group on one side, such as N, N-dimethyl-1,3-propanediamine and N, N diethyl 1,3-propanediamine, are used as the terminal of the urethane resin. It is preferably used for introducing a cationic group into.

The amount of the compound (h) having an active hydrogen capable of reacting with an isocyanato group varies depending on whether the compound is added together with the polyamino compound (e ') or added last alone. Is preferably 0.5 mol or less, more preferably 0.3 m, relative to 1 mol of the isocyanato group in the compound having an isocyanato group.
The amount is preferably not more than ol and is 0.5 to 3.0 mol per 1 mol of the isocyanate group which is finally present when it is added alone at the end, especially when the purpose is to stabilize the resin. Is preferably 1 to 3.0 mol.

Outside this range, adverse effects such as deterioration of film forming property and discoloration are observed. The end point of the reaction is judged by the isocyanate% measurement by titration and the disappearance of the isocyanate peak by IR measurement.

The molecular weight of the urethane resin is not particularly limited depending on the application, but is preferably 1,000 to 20 in terms of standard polystyrene equivalent weight average molecular weight by GPC.
10,000 is preferable. More preferably from 5,000
It is 150,000. Also, as the number average molecular weight,
It is preferably 1,000 to 150,000, more preferably 4,000 to 100,000. If it is larger than this, the viscosity becomes too high and it becomes difficult to handle. Conversely, if it is smaller than this, the performance as a polymer cannot be exhibited.

The viscosity of the resulting urethane resin solution is not particularly limited and is selected depending on the use of the resin, but it is preferably 10 to 10,000 mPa · s (25 ° C.) and used as an adhesive. In this case, more preferably 500 to 5,000 mPa ·
s (25 ° C.). If the viscosity is too high, the coating process may be difficult, and if it is too low, a resin having a sufficient molecular weight may not be formed.

(Curing Agent (D)) In the present invention, the urethane resin becomes a pressure-sensitive adhesive having a high cohesive force when the curing agent (D) is used together.

As the curing agent (D) used in the present invention, the above polyisocyanate (b) can be used.

The compounding ratio of the urethane resin and the curing agent (D) used in the present invention is 0.1 to 10 parts by weight of the curing agent (D) with respect to 100 parts by weight of the urethane resin. Curing agent (D)
If less than 0.1 part by weight, the cohesive force will be reduced and 10
If the amount is more than the amount by weight, the adhesive strength will decrease. Preferably 1
~ 5 parts by weight.

For the compounding, a known compounding method can be used. (Regarding Additives) In the present invention, the urethane resin may contain an organic / inorganic filler for the purpose of improving printability and coating film properties.

In the present invention, the organic filler is a natural product such as starch, acrylic such as polymethylmethacrylate, polystyrene, styrene-acrylic, nylon 6, such as nylon 6, nylon 12, nylon 6-12, high Examples include olefin-based, polyester-based, phenol-based, and benzoguanamine-based resin fine particles such as high-density polyethylene, low-density polyethylene, polypropylene, and tetrafluoroethylene.

In the present invention, the inorganic filler is clay,
Diatomaceous earth, aluminum silicate, calcium silicate, magnesium silicate, hydrotalcite, talc, kaolin, calcined kaolin, barium sulfate, titanium dioxide, calcium sulfate, light calcium carbonate, heavy calcium carbonate, magnesium hydroxide, magnesium carbonate, titanium oxide. , Zinc carbonate, zinc oxide, zinc hydroxide, zinc sulfide, lead oxide, zirconium oxide, magnesium oxide, synthetic amorphous silica, colloidal silica, alumina, alumina sol,
Inorganic fillers such as pseudo-boehmite, aluminum hydroxide, lithopone, zeolite and montmorillonite can be mentioned. When alumina sol or colloidal silica is used as the filler component, the urethane resin is made water-based by the above-mentioned method and then the filler is mixed to obtain a stable mixed liquid.

Further, 1) When a compound having a hydroxyl group or a carboxyl group is used as the compound (h) having an active hydrogen capable of reacting with an isocyanato group, 2) As a compound (h) having an active hydrogen capable of reacting with an isocyanato group. When a compound having an alkoxysilyl group is used, the obtained urethane resin can be grafted on the filler. Urethane resin is hydroxyl group,
In the case of having a carboxyl group or an epoxy group, the silane coupling agent (i) is added to the mixed liquid of the resin and the filler, and the mixture can be grafted by heating and stirring at 40 to 100 ° C. for 10 minutes to 3 hours. When the urethane resin has a methylol group or an N-alkoxymethyl group, grafting can be performed by heating and stirring a mixed solution of the resin and the filler in the presence of an acid catalyst, if necessary. When the urethane resin has an alkoxysilyl group, grafting can be performed by heating and stirring a mixed liquid of the resin and the filler at 40 to 100 ° C. for 10 minutes to 3 hours.

In the case of grafting a urethane resin onto alumina sol or colloidal silica, it is preferable to hydrophilize by the above-mentioned method and then mix the filler, or to hydrophilize during the grafting reaction to obtain a stable graft body.

The blending ratio of the filler and the urethane resin varies depending on the purpose of blending the filler, but for the purpose of, for example, preventing blocking or improving the mechanical properties of the coating film, the total amount of the coating agent is used as a standard, Preferably 5 to 50
%, And more preferably 10 to 40% by weight, and if it is more than 40% by weight, mechanical properties of the coating film, particularly bending property and extensibility, are deteriorated. Further, for the purpose of improving the drying property of the ink, it is preferably 50 to 95% by weight, more preferably 60 to 90% by weight, and if it is less than this, sufficient effect cannot be obtained. If the filler content is high,
Grafting a filler with a resin is preferable because the mechanical properties of the coating film are dramatically improved.

In the present invention, the urethane resin is used for the purpose of preventing blocking, curling, adjusting surface gloss, improving weather resistance, improving wettability of ink droplets, etc.
For example, acrylic resin, polyamide, epoxy resin, polyurethane resin, polyvinyl acetate, polyvinyl acetal, polystyrene, fluorine resin, polycarbonate, polyether, polyisobutylene, petroleum resin, rosin, nitrocellulose, sucrose ester, vinyl chloride / vinyl acetate copolymer Polymer, ethylene / vinyl acetate copolymer, α
-Olefin / maleic anhydride type copolymer, styrene /
Other than thermoplastic resins such as maleic anhydride copolymers, phenol resins, urea resins, melamine resins, amino resins, polyester resins, alkyd resins, silicon resins, epoxy resins, epoxy acrylate, polyester acrylate, urethane acrylate, poly One kind or two or more kinds of resins, such as ether acrylate and phosphazene resin, which are hardened by ultraviolet rays or electron beams can be blended within a range not hindering the object of the present invention.

Further, if necessary, a filler such as talc, calcium carbonate or titanium oxide, a tackifier, a UV absorber, a fluorescent dye such as a fluorescent brightener, a coloring dye, a coloring agent, a thickener, a decolorizing agent Additives such as a foaming agent, a leveling agent, an anti-crater agent, an anti-settling agent, an antioxidant, a light stabilizer, a flame retardant, a wax, and a heat stabilizer can be appropriately added alone or in combination of two or more kinds.

As the deterioration inhibitor used in the present invention, at least one selected from the group consisting of an antioxidant, an ultraviolet absorber and a light stabilizer is used.

Examples of the antioxidant used in the present invention include a radical chain inhibitor (primary antioxidant) and a peroxide decomposing agent (secondary antioxidant).

Examples of the radical chain inhibitor (primary antioxidant) include phenolic antioxidants and amine antioxidants.

Examples of the peroxide decomposing agent (secondary antioxidant) include sulfur type antioxidants and phosphorus type antioxidants.

Examples of phenolic antioxidants include monophenolic antioxidants, bisphenolic antioxidants, and polymeric phenolic antioxidants.

As the monophenol type antioxidant,
2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearin-β- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate, and the like.

As the bisphenol type antioxidant,
2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-)
6-t-butylphenol), 4,4′-thiobis (3
-Methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis [1,1-dimethyl-2- [β-
(3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-
And tetraoxaspiro [5.5] undecane.

Examples of the polymeric phenolic antioxidant include 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4. , 6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis-
[Methylene-3- (3 ', 5'-di-t-butyl-4'
-Hydroxyphenyl) propionate] methane, bis [3,3'-bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ', 5) '-Di-t-butyl-4'-hydroxybenzyl) -S-triazine-2,
4,6- (1H, 3H, 5H) trione, tocophenol, and the like. IRGANOX L 135 (Ciba Specialty Chemicals Co., Ltd.) is particularly preferable because of its compatibility with resins.

As sulfur type antioxidants, dilauryl 3,3'-thiodipropionate, dimyristyl 3,
3'-thiodipropionate, distearyl 3,3'-
Thiodipropionate and the like can be mentioned.

Examples of phosphorus antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, and the like.

Examples of the ultraviolet absorber used in the present invention include benzophenone-based, benzotriazole-based, salicylic acid-based, oxalic acid anilide-based, cyanoacrylate-based, and triazine-based ultraviolet absorbers.

As the benzophenone type ultraviolet absorber,
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
Octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-
4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane, Etc. can be mentioned.

As the benzotriazole type ultraviolet absorber, 2- (2'-hydroxy-5'-methylphenyl) is used.
Benzotriazole, 2- (2'-hydroxy-5'-
tert-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) 5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl)
Benzotriazole, 2- (2'-hydroxy-4'-
Octoxyphenyl) benzotriazole, 2- [2 '
-Hydroxy-3 '-(3 ", 4", 5 ",
6 '',-tetrahydrophthalimidomethyl) -5'-
Methylphenyl] benzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl)
-6- (2H-benzotriazol-2-yl) phenol], [2 (2'-hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole and the like can be mentioned. TUNUVIN 571 (Ciba Specialty Chemicals Co., Ltd.) is particularly preferable because of its compatibility with resins.

Examples of salicylic acid-based ultraviolet absorbers include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and the like.

Examples of the cyanoacrylate type ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-.
Diphenyl acrylate, etc. can be mentioned.

Examples of the light stabilizer used in the present invention include light stabilizers such as hindered amine light stabilizers and ultraviolet light stabilizers.

As the hindered amine light stabilizer,
[Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate], bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,
2,6,6-Pentamethyl-4-piperidyl sebacate can be mentioned. The product name is TINUVI
N 765 (Ciba Specialty Chemicals Co., Ltd.), ADEKA STAB LA-77 (Asahi Denka), Chima
sosorb 944LD (Ciba Specialty Chemicals Co., Ltd.), TINUVIN 622LD (Ciba Specialty Chemicals Co., Ltd.), TINUV
IN 144 (Ciba Specialty Chemicals Co., Ltd.), ADEKA STAB LA-57 (Asahi Denka), ADEKA STAB LA-62 (Asahi Denka), ADEKA STAB LA-67
(Asahi Denka), ADEKA STAB LA-63 (Asahi DENKA), ADEKA STAB LA-68 (Asahi DENKA), ADEKA STAB LA-8
2 (Asahi Denka), ADEKA STAB LA-87 (Asahi Denka), G
goodrite UV-3034 (Goodrich)
Can be mentioned. TINUVIN 765 (Ciba Specialty Chemicals Co., Ltd.) is particularly preferable because of its compatibility with resins.

As the UV stabilizer, nickel bis (octylphenyl) sulfide, [2,2'-thiobis (4-tert-octylphenolate)]-n-butylamine nickel, nickel complex-3,5-
Di-tert-butyl-4-hydroxybenzyl-phosphate monoethylate, nickel-dibutyldithiocarbamate, benzoate type quencher, nickel-
Dibutyldithiocarbamate and the like can be mentioned.

[0187] As the deterioration inhibitor, it is preferable to include an antioxidant and an ultraviolet absorber or a light stabilizer, and it is preferable to further include all of the antioxidant, the ultraviolet absorber and the light stabilizer. TINUVIN B 75 (Ciba Specialty Chemicals Co., Ltd.) is IRGANOX
L 135 (Ciba Specialty Chemicals Co., Ltd.), TINUVIN 571 (Ciba Specialty Chemicals Co., Ltd.) and TINUVIN 765 (Ciba Specialty Chemicals Co., Ltd.),
It is preferable that they can be used without their mutual effects interfering with each other.
The amount used is preferably 0 to 10% by weight of the solid content.

[0188]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Synthesis examples are shown below.

[0190]

Synthesis Example 1 Isophorone diamine (IPD was added to a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
A) 400 g and toluene 400 g were charged, and 4-hydroxybutyl acrylate 678 g was added dropwise at room temperature. After completion of dropping, the mixture was reacted at 80 ° C. for 1 hour and then toluene 678
The compound to which g is added is referred to as compound (1).

Synthesis Example 2 Isophorone diamine (IPD was added to a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
A) 400 g and toluene 400 g were charged, 4-hydroxybutyl acrylate 339 g, butyl acrylate 3
01 g was added dropwise at room temperature. After completion of the dropping, the mixture is reacted at 80 ° C. for 1 hour and then 640 g of toluene is added to obtain a compound (2).

Synthesis Example 3 Isophoronediamine (IPD was added to a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
A) 400 g, 400 g of toluene were charged, 169 g of 4-hydroxybutyl acrylate, butyl acrylate 4
52 g was added dropwise at room temperature. After completion of the dropping, the mixture is reacted at 80 ° C. for 1 hour and then 621 g of toluene is added to obtain a compound (3).

Synthesis Example 4 Isophorone diamine (IPD was added to a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
A) 400 g and toluene 400 g were charged, and butyl acrylate 602 g was added dropwise at room temperature. 80 after dropping
After reacting at 0 ° C. for 1 hour, 602 g of toluene was added to obtain a compound (4).

Synthesis Example 5 Kuraray Polyol C-1090 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
(Bifunctional polycarbonate diol, OH value 112, manufactured by Kuraray Co., Ltd.) 675 g, isophorone diisocyanate (manufactured by Huls Japan 225 g), toluene 225 g, dibutyltin dilaurate 0.07 as a catalyst.
Charge 5 g, gradually raise the temperature to 100 ° C., and carry out the reaction for 2 hours. After confirming the remaining amount of isocyanato group by titration, 40 ℃
After cooling to 1647 g of ethyl acetate and 8.1 g of acetylacetone, 258 g of compound (1) dissolved in 180 g of ethyl acetate was added dropwise over 1 hour, and after aging for 1 hour, 2-amino-2-methyl -3.3 g of propanol (manufactured by Nagase & Co., Ltd.) was added, and it was confirmed that the NCO characteristic absorption (2270 cm-1) on the IR chart had disappeared, and the reaction was terminated. The reaction solution was colorless and transparent, had a solid content of 32%, a viscosity of 4,500 cps, a number average molecular weight of MN43,000, and a weight average molecular weight of MW133,000.
Met.

Synthesis Example 6 Kuraray Polyol C-1090 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
(Bifunctional polycarbonate diol, OH value 112, manufactured by Kuraray Co., Ltd.) 675 g, isophorone diisocyanate (manufactured by Huls Japan 225 g), toluene 225 g, dibutyltin dilaurate 0.07 as a catalyst.
Charge 5 g, gradually raise the temperature to 100 ° C., and carry out the reaction for 2 hours. After confirming the remaining amount of isocyanato group by titration, 40 ℃
After cooling to 1857 g of ethyl acetate and 8.1 g of acetylacetone, 262 g of compound (2) dissolved in 180 g of ethyl acetate was added dropwise over 1 hour and aged for 1 hour, and then 2-amino-2-methyl. -Propanol (Nagase Sangyo Co., Ltd.) 5.5 g was added, and it was confirmed that the NCO characteristic absorption (2270 cm -1) on the IR chart had disappeared, and the reaction was terminated. This reaction solution was colorless and transparent, had a solid content of 30%, a viscosity of 13,400 cps, a number average molecular weight of MN63,300, and a weight average molecular weight of MW185,70.
It was 0.

Synthesis Example 7 Kuraray Polyol C-1090 was placed in a 4-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer and a dropping funnel.
(Bifunctional polycarbonate diol, OH value 112, manufactured by Kuraray Co., Ltd.) 675 g, isophorone diisocyanate (manufactured by Huls Japan 225 g), toluene 225 g, dibutyltin dilaurate 0.07 as a catalyst.
Charge 5 g, gradually raise the temperature to 100 ° C., and carry out the reaction for 2 hours. After confirming the remaining amount of isocyanato group by titration, 40 ℃
After cooling to 1854 g of ethyl acetate and 8.1 g of acetylacetone, 260 g of compound (3) dissolved in 180 g of ethyl acetate was added dropwise over 1 hour, and after aging for 1 hour, 2-amino-2-methyl -3.3 g of propanol (manufactured by Nagase & Co., Ltd.) was added, and it was confirmed that the NCO characteristic absorption (2270 cm-1) on the IR chart had disappeared, and the reaction was terminated. The reaction solution was colorless and transparent, had a solid content of 30%, a viscosity of 6,700 cps, a number average molecular weight of MN35,700, and a weight average molecular weight of MW124,700.
Met.

Synthesis Example 8 Kuraray Polyol C-1090 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer and a dropping funnel.
(Bifunctional polycarbonate diol, OH value 112, manufactured by Kuraray Co., Ltd.) 248 g, Kuraray polyol C-20
90 (bifunctional polycarbonate diol, OH value 56.
9, 475 g of Kuraray Co., Ltd., 165 g of isophorone diisocyanate (manufactured by Huls Japan KK), 225 g of toluene, and 0.075 g of dibutyltin dilaurate as a catalyst are charged, and the temperature is gradually raised to 100 ° C. and the reaction is carried out for 2 hours. After confirming the remaining amount of the isocyanato group by titration, the mixture was cooled to 40 ° C., 2052 g of ethyl acetate and 8.1 g of acetylacetone were added, and then 191 g of compound (2) dissolved in 180 g of ethyl acetate was added dropwise over 1 hour, and further. After aging for 1 hour, 3.3 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added to give I.
It was confirmed that the NCO characteristic absorption (2270 cm -1) on the R chart had disappeared and the reaction was terminated. The reaction solution was colorless and transparent, had a solid content of 28%, a viscosity of 10,200 cps, a number average molecular weight of MN63,000, and a weight average molecular weight of MW18.
It was 4,600.

Synthesis Example 9 Kuraray Polyol C-2090 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
(Bifunctional polycarbonate diol, OH value 56.9,
(Kuraray Co., Ltd.) 770 g, isophorone diisocyanate (Huls Japan KK) 130 g, toluene 225 g, dibutyltin dilaurate 0.0 as a catalyst
75 g is charged, the temperature is gradually raised to 100 ° C., and the reaction is performed for 2 hours. After checking the remaining amount of isocyanato group by titration,
The mixture was cooled to 0 ° C., 2052 g of ethyl acetate and 8.1 g of acetylacetone were added, and then 152 g of compound (2) dissolved in 180 g of ethyl acetate was added dropwise over 1 hour, followed by aging for 1 hour, and then 2-amino-2-. 3.3 g of methyl-propanol (manufactured by Nagase & Co., Ltd.) was added, and it was confirmed that the NCO characteristic absorption (2270 cm-1) on the IR chart had disappeared, and the reaction was terminated. The reaction solution was colorless and transparent and had a solid content of 30%, a viscosity of 16,800 cps, a number average molecular weight of MN64,500 and a weight average molecular weight of MW186,00.
It was 0.

Synthesis Example 10 Kuraray polyol PMSA-1 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
000 (bifunctional polycarbonate diol, OH value 11
5, 670 g of Kuraray Co., Ltd., 230 g of isophorone diisocyanate (manufactured by Huls Japan KK), 225 g of toluene, and 0.075 g of dibutyltin dilaurate as a catalyst are charged, and the temperature is gradually raised to 100 ° C. and the reaction is carried out for 2 hours. After confirming the remaining amount of the isocyanato group by titration, the mixture was cooled to 40 ° C., 1656 g of ethyl acetate and 8.1 g of acetylacetone were added, and 260 g of compound (1) dissolved in 180 g of ethyl acetate was added dropwise over 1 hour, and After aging for 1 hour, 5 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added, and it was confirmed that the NCO characteristic absorption (2270 cm-1) on the IR chart had disappeared, and Carbodilite V was used. -07 (manufactured by Nisshinbo Industries Inc.) was added to terminate the reaction. This reaction solution is colorless and transparent, has a solid content of 32% and a viscosity of 4,900 cp.
s, number average molecular weight MN49,500, weight average molecular weight M
It was W163,000.

Synthesis Example 11 Polyether polyol PP-is placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer and a dropping funnel.
1000 (bifunctional polyether polyol, OH number 11
2, manufactured by Sanyo Chemical Industry Co., Ltd.) 675 g, isophorone diisocyanate (manufactured by Huls Japan KK) 225
g, 225 g of toluene, and 0.075 g of dibutyltin dilaurate as a catalyst are charged, the temperature is gradually raised to 100 ° C., and the reaction is performed for 2 hours. After confirming the amount of isocyanato group remaining by titration, the mixture was cooled to 40 ° C., and after adding 2543 g of ethyl acetate and 8.1 g of acetylacetone, 180 g of ethyl acetate
268 g of the compound (2) dissolved in
After further aging for 1 hour, 1.8 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added,
It was confirmed that the NCO characteristic absorption (2270 cm -1) on the IR chart had disappeared, and the reaction was terminated. The reaction solution was colorless and transparent and had a solid content of 25%, a viscosity of 600 cps, a number average molecular weight of MN13,400, and a weight average molecular weight of MW91,8.
It was 00.

Synthesis Example 12 Polyester polyol P-1 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
010 (bifunctional polyester polyol, OH number 11
2. 675 g of Kuraray Co., Ltd., 225 g of isophorone diisocyanate (manufactured by Huls Japan KK), 225 g of toluene, and 0.075 g of dibutyltin dilaurate as a catalyst are charged, and the temperature is gradually raised to 100 ° C. and the reaction is carried out for 2 hours. After confirming the residual amount of the isocyanato group by titration, the mixture was cooled to 40 ° C., 1863 g of ethyl acetate and 8.1 g of acetylacetone were added, and then 220 g of the compound (1) dissolved in 180 g of ethyl acetate was added dropwise over 1 hour. After aging for 1 hour, 4.1 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added to give I.
After confirming that the NCO characteristic absorption (2270 cm -1) on the R chart disappeared, 9 g of Carbodilite V-09 (manufactured by Nisshinbo Industries Inc.) was added to terminate the reaction. The reaction solution is colorless and transparent, has a solid content of 30% and a viscosity of 1,400c.
ps, number average molecular weight MN49,100, and weight average molecular weight MW119,400.

Synthesis Example 13 Kuraray Polyol C-1090 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
(Bifunctional polycarbonate diol, OH value 112, manufactured by Kuraray Co., Ltd.) 675 g, isophorone diisocyanate (manufactured by Huls Japan 225 g), toluene 225 g, dibutyltin dilaurate 0.07 as a catalyst.
Charge 5 g, gradually raise the temperature to 100 ° C., and carry out the reaction for 2 hours. After confirming the remaining amount of isocyanato group by titration, 40 ℃
After cooling to 518 g of ethyl acetate and 8.1 g of acetylacetone, 21.5 g of 2-hydroxyethylaminopropylamine (manufactured by Koei Chemical Industry Co., Ltd.) dissolved in 180 g of ethyl acetate was added dropwise over 1 hour. After aging for 1 hour, 7.9 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added, and it was confirmed that the NCO characteristic absorption (2270 cm -1) on the IR chart had disappeared and the reaction was completed. Finished. The reaction solution was colorless and transparent and had a solid content of 50%, a viscosity of 4,200 cps, a number average molecular weight MN22,400, and a weight average molecular weight MW61,60.
It was 0.

Synthesis Example 14 Kuraray polyol PMSA-1 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
000 (bifunctional polycarbonate diol, OH value 11
5, 670 g of Kuraray Co., Ltd., 230 g of isophorone diisocyanate (manufactured by Huls Japan KK), 225 g of toluene, and 0.075 g of dibutyltin dilaurate as a catalyst are charged, and the temperature is gradually raised to 100 ° C. and the reaction is carried out for 2 hours. After confirming the residual amount of the isocyanato group by titration, the mixture was cooled to 40 ° C., 555 g of ethyl acetate and 8.1 g of acetylacetone were added, and then MXDA-PO2 (manufactured by Mitsubishi Gas Chemical Co., Inc.) dissolved in 180 g of ethyl acetate.
After dropping 65 g in 1 hour and aging for 1 hour, 2
-Amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) (5.5 g) was added, and it was confirmed that the NCO characteristic absorption (2270 cm-1) on the IR chart had disappeared, and Carbodilite V-07 (Nisshinbo Industries, Inc.) The reaction was completed by adding 9 g (made by Co., Ltd.). The reaction solution was colorless and transparent, had a solid content of 50%, a viscosity of 1,300 cps, and a number average molecular weight of MN2.
It was 1,000 and the weight average molecular weight was MW65,000.

Synthesis Example 15 Kuraray polyol C-1090 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer and a dropping funnel.
(Bifunctional polycarbonate diol, OH value 112, manufactured by Kuraray Co., Ltd.) 675 g, isophorone diisocyanate (manufactured by Huls Japan 225 g), toluene 225 g, dibutyltin dilaurate 0.07 as a catalyst.
Charge 5 g, gradually raise the temperature to 100 ° C., and carry out the reaction for 2 hours. After confirming the remaining amount of isocyanato group by titration, 40 ℃
After cooling to 1859 g of ethyl acetate and 8.1 g of acetylacetone, 259 g of compound (2) dissolved in 180 g of ethyl acetate was added dropwise over 1 hour, and after aging for 1 hour, 3-aminopropyltriethoxysilane was added. 0.9 g (manufactured by Nippon Unicar Co., Ltd.) was added and aged for 10 minutes, and then 3.6 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added to the NCO characteristic absorption ( 2270 cm -1) was confirmed to have disappeared, and the reaction was terminated. This reaction solution was colorless and transparent, had a solid content of 30%, a viscosity of 4,400 cps, a number average molecular weight of MN56,300, and a weight average molecular weight of MW143,9.
It was 00.

Synthesis Example 16 Kuraray polyol C-1090 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer and a dropping funnel.
(Bifunctional polycarbonate diol, OH value 112, manufactured by Kuraray Co., Ltd.) 675 g, isophorone diisocyanate (manufactured by Huls Japan 225 g), toluene 225 g, dibutyltin dilaurate 0.07 as a catalyst.
Charge 5 g, gradually raise the temperature to 100 ° C., and carry out the reaction for 2 hours. After confirming the remaining amount of isocyanato group by titration, 40 ℃
After cooling to 1859 g of ethyl acetate and 8.1 g of acetylacetone, 259 g of compound (2) dissolved in 180 g of ethyl acetate was added dropwise over 1 hour, and after aging for 1 hour, 2-amino-2-methyl -Add 5.5 g of propanol (made by Nagase & Co., Ltd.) and confirm that the NCO characteristic absorption (2270 cm-1) on the IR chart has disappeared, and then add 0.9 g of γ-isocyanatopropyltriethoxysilane. Temperature up to 100 ° C,
After reacting for 15 minutes, the reaction was completed. The reaction solution was colorless and transparent, had a solid content of 30%, a viscosity of 5,400 cps, a number average molecular weight of MN64,500, and a weight average molecular weight of MW15.
It was 3,700.

Synthesis Example 17 Polyether polyol PP- was added to a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH number 5
4.7, manufactured by Sanyo Chemical Industries, Ltd.) 774 g, isophorone diisocyanate (manufactured by Huls Japan KK) 1
26 g of toluene, 225 g of toluene, and 0.075 g of dibutyltin dilaurate as a catalyst are charged, the temperature is gradually raised to 100 ° C., and the reaction is performed for 2 hours. After confirming the remaining amount of the isocyanato group by titration, the mixture was cooled to 40 ° C., 486 g of ethyl acetate and 8.1 g of acetylacetone were added, and then ethyl acetate 180 was added.
Compound (4) 107 g dissolved in g was added dropwise over 1 hour, and after aging for 1 hour, 2.9 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added to the IR chart. NCO characteristic absorption (2270cm-1)
Was confirmed to have disappeared, and the reaction was terminated. The reaction solution is colorless and transparent, solid content 50%, viscosity 8,600 cp
s, number average molecular weight MN32,200, weight average molecular weight M
It was W82,900.

Synthesis Example 18 Butyl acrylate 22 was added to a 2 liter reactor equipped with a stirrer, condenser, thermometer, and nitrogen introducing tube.
2 parts, methyl acrylate 62 parts, acrylic acid 25 parts, ethyl acetate 34 parts, azobisisobutyronitrile 0.08
Four parts were charged and nitrogen substitution was carried out for 30 minutes or more. Separately, 222 parts of butyl acrylate, 62 parts of methyl acrylate, 25 parts of acrylic acid, 584 parts of ethyl acetate, and 0.084 part of azobisisobutyronitrile were prepared in a dropping funnel. After that, the temperature of the reactor was raised, and when the temperature reached 60 ° C., the contents of the dropping funnel were added dropwise to start the reaction. The dropping was completed in 1 hour, and 0.168 parts of azobisisobutyronitrile was added 2 hours and 3 hours after the start of the reaction,
Further, stirring was continued for 5 hours to obtain a resin composition. Polymerization was performed while maintaining the outer wall of the reactor at 60 ° C. The obtained high molecular weight polymer had a polymerization average molecular weight of 1.38 million and a molecular weight distribution of 4.3.
Met.

Adhesive Effects Example 1 0.64 g of a curing agent (D) was added to 100 g of the urethane resin solution synthesized in Synthesis Example 5, and the adhesive strength and the optical property retention after a heat resistance test were determined by a predetermined method. The moisture and heat resistance test was measured. As the curing agent (D), a 75 wt% ethyl acetate solution of hexamethylene diisocyanate trimethylolpropane adduct was used. (0.48 g of hexamethylene diisocyanate, which is 1.5% by weight of 32 g of urethane resin, was added.) The test method is as follows.

<Coating method> 20 g / m ² of the above urethane resin solution was coated on a release paper with an applicator, and the temperature was kept at 100 ° C.
It was dried for 2 minutes to prepare a coated product. After one week at room temperature, it was used for the following measurements.

<Adhesiveness> An adhesive sheet obtained by coating a release paper with a urethane resin solution was transferred to a polyethylene terephthalate film (film thickness 25 μm), and it was placed on a stainless steel plate (SUS304) having a thickness of 0.4 mm at 23 ° C. and 65%. After sticking by RH and roll-pressing according to JIS, 20 minutes later, peel strength (180 degree peeling, pulling speed 300 mm / min; unit g / 25 mm width) was measured by a Shopper type peeling tester.

<Optical Property Maintainability after Heat Resistance Test> An adhesive film obtained by coating a release paper with a urethane resin solution was transferred onto one side of a polarizing film to obtain an optical film. This optical film having a size of 194 mm × 250 mm was adhered to the both sides of a glass plate having a thickness of 1.1 mm through the adhesive layer so that the absorption axes were orthogonal to each other on the front and back sides, and the film was placed in an autoclave at 50 ° C. and 5 atmospheric pressure for 30 minutes. After leaving it for a minute to mature the adhesion state, it was heated in an atmosphere of 90 ° C. for 500 hours, and the presence or absence of a decrease in the degree of polarization affecting visibility was checked on the backlight, and the judgment was made according to the following criteria.

◯: When the decrease in the degree of polarization that affects the visibility is not recognized as a whole Δ: When a slight decrease in the degree of polarization that affects the visibility is recognized at the ends ×: Polarized light that affects the visibility When a decrease in degree is observed

<Moisture and heat resistance test> An adhesive film obtained by coating a release paper with a urethane resin solution was transferred onto one surface of a polarizing film to obtain an optical film. 250m of this optical film
m × 350 mm size, adhered to a 1.1 mm-thick glass plate through the pressure-sensitive adhesive layer, left in an autoclave at 50 ° C. and 5 atm for 30 minutes to age the bonded state, and then 60 ° C. 90% Hold for 500 hours in RH atmosphere,
It was judged according to the following criteria.

[0215] ◎: When no floating, peeling, or foaming is observed ◯: Floating at the edge and slight peeling was observed ×: When floating, peeling, or foaming was observed

Examples 2 to 22 and Comparative Examples 1 to 2 The urethane resin was changed to that shown in Table 1, and the curing agent (D) was used.
By changing the addition amount of
To 20 was added 0.1 g of the silane coupling agent (i) or the alkoxysilane shown in Table 1. later,
The same operation as in Example 1 was performed. Table 1 also shows the solid content of the urethane resin, the adhesive strength, the optical property retention after the heat resistance test, the result of the moist heat resistance test, and the concentration of the hydroxyl group contained in R ³ .

Calculation Method of Concentration of Hydroxyl Group Contained in R ^{3 The} number of moles of hydroxyl group compounded is calculated from the compounding amount of the hydroxyl group-containing acrylic monomer or hydroxyl group-containing amine used in the synthesis. This value is divided by the total amount of the resin component to calculate the hydroxyl group concentration contained in R ³ .

[0218]

[Table 1]

[0219]

[0220]

Industrial Applicability According to the present invention, it is possible to provide a pressure-sensitive adhesive suitable for bonding a polarizing plate, which hardly causes deterioration of optical properties, a method for producing the same, a pressure-sensitive adhesive sheet, and a laminate.

Continued front page    F term (reference) 2H049 BA02 BB52 BC22                 4J034 BA08 CA04 CA05 CB03 CB04                       CC06 DA01 DB04 DC06 DC07                       DC12 DC35 DC43 DF01 DF02                       DF12 DF16 DF17 DF20 DF22                       DG03 DG04 DG05 DG10 DG12                       HA01 HA07 HA08 HC03 HC12                       HC22 HC46 HC52 HC61 HC64                       HC65 HC67 HC70 HC71 HC73                       JA42 KB04 KC16 KC17 KC18                       KC35 KD02 KD04 KE02 QA02                       QB10 QB15 QC05 RA08                 4J040 EF001 EF051 EF061 EF111                       EF121 EF131 EF291 EF301                       EH011 GA31 HC16 KA10                       NA17

Claims (11)

[Claims] 1. A compound synthesized from a raw material containing a polyamino compound (e ′) having a hydroxyl group, a polyisocyanate (b), and a polyol (a), and having a bonding site represented by the following formula (1) and a urethane group. A pressure-sensitive adhesive comprising a urethane resin composition having a hydroxyl group concentration of R ³ of 1 × 10 ⁻⁵ mol / g to 1 × 10 ⁻³ mol / g. Formula (1) —R ¹ —N (R ³ ) —CO—NH—R ² — (In the formula (1), R ¹ is a polyamino compound (e ′)-derived divalent organic residue having an amino group. The group, R ² represents a polyvalent organic residue derived from the polyisocyanate (b), and R ³ represents a monovalent organic residue derived from the polyamino compound (e ′) and containing at least one hydroxyl group.) 2. The pressure-sensitive adhesive according to claim 1, wherein the urethane resin composition further contains an alkoxysilyl group. 3. A pressure-sensitive adhesive comprising a urethane resin composition, which is 20 g / m of a mixture obtained by adding 1.5 parts by weight of hexamethylene diisocyanate trimethylolpropane adduct to 100 parts by weight of the urethane resin composition.
² is applied onto an optical film to form a urethane resin pressure-sensitive adhesive layer, and the optical film is bonded to both sides of the glass plate through the urethane resin pressure-sensitive adhesive layer so that the absorption axes are orthogonal to each other at 50 ° C., Leave it in an autoclave at 5 atm for 30 minutes and heat it in an atmosphere at 1 atm 90 ° C for 500 hours.
Adhesion that can give a glass plate to which the two optical films are adhered, which has substantially no decrease in the polarization degree that affects visibility when a backlight is passed through the glass plate to which the two optical films are adhered. Agent. 4. The pressure-sensitive adhesive according to claim 1, wherein the polyamino compound (e ′) is a compound obtained by subjecting a polyamine (e) and a compound (f) having an unsaturated group to a Michael addition reaction. 5. The pressure-sensitive adhesive according to claim 1, wherein the polyamino compound (e ′) is a compound (d) represented by the following formula (2). Formula (2) (In the formula (2), Y represents a monovalent hydrocarbon group containing one or more functional groups having active hydrogen, but may contain NH in the main chain. N represents 0 or 1. , R ⁴ and R
⁵ independently represents a hydrogen atom or a monovalent hydrocarbon group containing no hydroxyl group, and R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent hydrocarbon group. ) 6. The pressure-sensitive adhesive according to claim 1,
A pressure-sensitive adhesive comprising a curing agent (D). 7. A laminate comprising a base material and the pressure-sensitive adhesive according to claim 1. 8. A method for producing a pressure-sensitive adhesive comprising a urethane resin composition, wherein the urethane resin composition comprises a polyol (a) and a polyisocyanate (b) in the presence of a catalyst (c). A method for producing a pressure-sensitive adhesive, which is a urethane resin (C ′) obtained by chain-extending a reaction polyurethane prepolymer (A) with a polyamino compound (e ′). 9. A method for producing a pressure-sensitive adhesive comprising a urethane resin, wherein the urethane resin is a polyol (a).
And a polyisocyanate (b) in the presence of a catalyst (c), a polyurethane prepolymer (A),
A urethane resin (C ") obtained by reacting a urethane resin having an isocyanate group at the terminal chain-extended with a polyamino compound (e ') and a compound (h) having active hydrogen capable of reacting with the isocyanato group. Method of manufacturing agent. 10. The method for producing a pressure-sensitive adhesive according to claim 9, wherein the compound (h) having active hydrogen capable of reacting with an isocyanato group contains a silane coupling agent (i) containing an alkoxysilyl group. 11. The method for producing a pressure-sensitive adhesive according to claim 8, wherein the polyamino compound (e ′) is a compound containing a hydroxyl group.