JP2011063792A - Curable composition, tacky material, tacky laminate, and method for manufacturing tacky material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition which is excellent in reactivity when curing, gives a good cured state, and has a longer pot life, and to provide a tacky material and a tacky laminate using the same. <P>SOLUTION: The curable composition includes a silyl group-containing polymer (S) which has a main chain of a polyether chain, a polyester chain and/or a polycarbonate chain, and a molecular end of a hydrolyzable silyl group; and a curing catalyst (A), with the curing catalyst (A) containing an iron-chelating compound (A1) and a metal compound (A2) except the iron-chelating compound. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a curable composition containing a silyl group-containing polymer having a hydrolyzable silyl group at a molecular terminal and a curing catalyst, an adhesive and an adhesive laminate using the curable composition, and the curable composition. The present invention relates to a method for producing a pressure-sensitive adhesive body using the composition.

Conventionally, organotin compounds such as dibutyltin dilaurate and dibutyltin diacetonate have been widely used as curing catalysts for curable resins having hydrolyzable silyl groups (for example, Patent Document 1).
Patent Document 2 describes a curable composition containing an organic polymer having a hydrolyzable silyl group, a titanium chelate, and a polymer plasticizer.

Japanese Patent No. 3030020 International Publication No. 2005/108491 Pamphlet

However, since the organic tin compound has a large environmental load, it is desired to reduce the amount used. In addition, since the reactivity is relatively large and the pot life is short, work restrictions become large.
On the other hand, a titanium chelate which is a non-organotin catalyst is relatively expensive. In addition, since the reactivity is inferior, there is a problem that the addition amount must be increased in order to obtain a preferable curing rate.

  The present invention has been made in view of the above circumstances, and is capable of adjusting the pot life to be long, and is excellent in reactivity at the time of curing and capable of obtaining a good cured state, and an adhesive using the same It is another object of the present invention to provide a pressure-sensitive adhesive laminate and a method for producing a pressure-sensitive adhesive body using the curable composition.

  In order to solve the above problems, the curable composition of the present invention comprises a silyl group-containing polymer having a polyether chain, a polyester chain, and / or a polycarbonate chain in the main chain and a hydrolyzable silyl group at the molecular end. A coalescence (S) and a curing catalyst (A) are contained, and the curing catalyst (A) contains an iron chelate compound (A1) and a metal compound (A2) other than the iron chelate compound.

The metal compound (A2) is one or more selected from the group consisting of calcium compounds, vanadium compounds, titanium compounds, potassium compounds, barium compounds, manganese compounds, nickel compounds, cobalt compounds, zirconium compounds, aluminum compounds and bismuth compounds. Preferably there is.
It is preferable that 0.001-10 mass parts of said hardening catalysts (A) are included with respect to 100 mass parts of said silyl group containing polymers (S).
The use ratio of the iron chelate compound (A1) and the metal compound (A2) is preferably 0.01 / 1 to 10/1 in terms of mass ratio (A1) / (A2).
The hydrolyzable silyl group is preferably a trialkoxysilyl group.

This invention provides the adhesive body formed by hardening | curing the curable composition of this invention.
This invention provides the adhesion laminated body which has the adhesion body layer which consists of an adhesion body of this invention on a base material.
This invention provides the manufacturing method of an adhesive body which has the process of heating and hardening the curable composition of this invention.

The curable composition of the present invention can adjust the pot life for a long time, and has excellent reactivity during curing and a good cured state. In addition, the curable composition of the present invention exhibits a good cured state on the surface and inside, and exhibits good removability. ADVANTAGE OF THE INVENTION According to this invention, while having the pot life of the curable composition to be used and showing the outstanding sclerosis | hardenability, the adhesive body and adhesive laminated body which have favorable removability can be provided.
The curable composition of this invention can manufacture an adhesive body preferably by the method which has the process of heating and hardening this.

The number average molecular weight (Mn) and the mass average molecular weight (Mw) in this specification are polystyrene-converted molecular weights obtained by measuring with gel permeation chromatography using a standard curve prepared using a standard polystyrene sample with a known molecular weight. It is.
The average hydroxyl value (OHV) in this specification is a measured value based on JIS-K-1557-6.4.
In the present specification, the polyether polyester polyol is a polyol having an ether bond and an ester bond.

In the present specification, the adhesion property is a property that adheres to an adherend with light pressure and can be re-peeled arbitrarily. An adhesive (pressure sensitive adhesive) is a substance that has adhesiveness and adheres to an adherend with light pressure. It has removability and is used for temporary adhesion. On the other hand, the adhesive is different from the pressure-sensitive adhesive in that it has permanent adhesive performance and does not have removability.
An adhesive substance is an adhesive compact. An adhesive sheet (also simply referred to as an adhesive sheet) (pressure sensitive adhesive sheet) is an adhesive sheet. However, in this specification, the thickness and the sheet are not distinguished from each other. The pressure-sensitive adhesive sheet is usually a laminate having at least a base material layer and a pressure-sensitive adhesive layer as components. An adhesive tape (also simply referred to as an adhesive tape) is a tape-shaped adhesive sheet.

In the present specification, pressure-sensitive adhesives may be classified according to the strength of peel adhesive strength (peel strength from the adherend). Slight adhesion when peel adhesion exceeds 0 N / 25 mm and less than 1 N / 25 mm, low adhesion when peel adhesion exceeds 1 N / 25 mm and less than 8 N / 25 mm, peel adhesion exceeds 8 N / 25 mm and 15 N / 25 mm The following cases are referred to as medium adhesion, and the case where the peel adhesive strength exceeds 15 N / 25 mm and is 50 N / 25 mm or less is called strong adhesion. Unless otherwise specified, the peel adhesive strength conforms to the 180-degree peeling method specified in JIS-Z-0237 (1999) -8.3.1 and follows the following test method.
That is, in a 23 ° C. environment, a 1.5 mm thick bright annealed stainless steel plate (SUS304 (JIS)) was attached to a pressure sensitive adhesive sheet test piece (width: 25 mm), and a rubber roll having a mass of 2 kg. Crimp. After 30 minutes, the peel strength (180 degree peel, tensile speed 300 mm / min) is measured using a tensile tester specified in JIS-B-7721. The value of the peel strength after 30 minutes of sticking obtained in this way is defined as “peel adhesive strength” in the present invention.

<Curable composition>
The curable composition of the present invention can be obtained by mixing a silyl group-containing polymer (S), a curing catalyst (A), an additive that is optionally blended as necessary.
<Silyl group-containing polymer (S)>
The silyl group-containing polymer (S) in the present invention has a polyether chain, a polyester chain, and / or a polycarbonate chain in the main chain and a hydrolyzable silyl group at the molecular end.
That is, the main chain of the silyl group-containing polymer (S) has one or two kinds selected from a polyether chain, a polyester chain, and a polycarbonate chain. In particular, the main chain preferably has a polyether chain, a polyester chain, a polycarbonate chain, or a combination of a polyether chain and a polyester chain.
The silyl group-containing polymer (S) is preferably any one of the following (S1) to (S3), or a mixture of two or more. In particular, (S1) is preferable since the obtained cured product is excellent in flexibility and wettability.
The silyl group-containing polymer (S) is not included in any of the following (S1) to (S3) and has a hydrolyzable silyl group (hereinafter referred to as “polymer having another hydrolyzable silyl group”). May be included.). 30 mass% or less of a silyl group containing polymer (S) is preferable, and, as for the ratio of the polymer which has another hydrolysable silyl group, 10 mass% or less is more preferable.

[Silyl group-containing polymer (S1)]
The silyl group-containing polymer (S1) is obtained by introducing a hydrolyzable silyl group into the terminal of one or more polyol compounds selected from the group consisting of polyether polyol, polyester polyol, polycarbonate polyol, and polyether polyester polyol. can get.
The silyl group-containing polymer (S1) is particularly preferably obtained by introducing a hydrolyzable silyl group into the polyol compound by the method described in any of (PQ1) to (PQ5) described later.

[Silyl group-containing polymer (S2)]
The silyl group-containing polymer (S2) is a polyurethane obtained by reacting at least one polyol compound selected from the group consisting of polyether polyol, polyester polyol, polycarbonate polyol, and polyether polyester polyol with a polyisocyanate compound. It is a silyl group-containing polymer obtained by introducing a hydrolyzable silyl group into the end of the prepolymer.
The silyl group-containing polymer (S2) is particularly preferably obtained by introducing a hydrolyzable silyl group into a polyurethane prepolymer by the method described in any of (PQ1) to (PQ5) described later.

[Silyl group-containing polymer (S3)]
The silyl group-containing polymer (S3) is a polyurethane obtained by reacting one or more polyol compounds selected from the group consisting of polyether polyol, polyester polyol, polycarbonate polyol, and polyether polyester polyol with a polyisocyanate compound. It is a silyl group-containing polymer obtained by introducing a hydrolyzable silyl group into the molecular terminal of a polyurethane polymer obtained by further subjecting the prepolymer to a chain extension reaction using a chain extender.
The silyl group-containing polymer (S3) is particularly preferably obtained by introducing a hydrolyzable silyl group into a polyurethane polymer by the method described in any of (PQ1) to (PQ5) described later.

[Polyol compound]
The polyether polyol in the present invention is a polyol having a polyether chain (—OR ¹ —) _n1 [R ¹ is an alkylene group having 2 to 4 carbon atoms, n1 is an integer of 1 to 1000], and has a polyester chain. Absent.
The polyester polyol has a polyester chain (—OC (O) —R ² —) _n2 [R ² is an alkylene group having 2 to 8 carbon atoms or an arylene group having 6 to 20 carbon atoms, and n 2 is an integer of 1 to 1000]. It is a polyol and does not have a polyether chain.
The polycarbonate polyol is a polycarbonate chain (—OC (O) —O—R ³ —) _n3 [R ³ is an alkylene group having 2 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, and n3 is an integer of 1 to 1000] The polyol has a polyether chain and a polyester chain.
The polyether polyester polyol is a polyol having both a polyether chain and a polyester chain.
As a polyol compound, only 1 type may be used and 2 or more types may be used together.

In particular, it is preferable to use at least one kind of polyol having a polyether skeleton from the viewpoint of securing the flexibility of the pressure-sensitive adhesive body. The polyol having a polyether skeleton means a polyol having a polyether chain, such as a polyether polyol and a polyether polyester polyol.
The fact that the pressure-sensitive adhesive body is flexible is considered to be effective for suppressing so-called zipping, a phenomenon in which a sound of crispness is generated without peeling off smoothly when peeling off the pressure-sensitive adhesive body from the adherend. Moreover, the viscosity of a curable composition can be made low by having a polyether skeleton. Furthermore, by having a polyether skeleton, the surface resistance of the pressure-sensitive adhesive body can be lowered, and peeling charge can be suppressed.
Moreover, you may use an oxyethylene group as a part of polyether chain, and when this is used, surface resistance can be made smaller. When using, the ratio of the octylene group in all the polyether chains is preferably 5 to 70% by mass, and more preferably 10 to 50% by mass. The oxyethylene group may be present in blocks in the polyether chain, or may be present at random.

The ratio of the ether bond (—OR ¹ —) in the silyl group-containing polymer (S) is 40% with respect to the total (100 mol%) of the ether bond and the ester bond (—OC (O) —R ² —). -100 mol% is preferable, 50-100 mol% is more preferable, and 60-100 mol% is further more preferable.
As the polyol compound for obtaining the silyl group-containing polymer (S), particularly when one or more polyols selected from polyether polyols and polyether polyester polyols are used, or from polyether polyols and polyether polyester polyols. It is preferable to use one or more selected polyols in combination with one or more polyols selected from polyester polyols and polycarbonate polyols. It is more preferable to use only polyether polyol, only polyether polyester polyol, or a combination of polyether polyol and polyether polyester polyol.

As the polyether polyol, polyoxyalkylene polyol is preferable.
Examples of the alkylene group constituting the polyoxyalkylene polyol include an ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, propylene group, butylene group, and methyltrimethylene group. These can be obtained by ring-opening polymerization of the corresponding cyclic ether compound. Examples of the cyclic ether compound include alkylene oxides that are epoxide compounds having a three-membered ring, oxetanes having a four-membered ring, tetrahydrofuran that is a five-membered ring, and tetrahydropyran that is a six-membered ring. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and the like. Examples of the polyoxyalkylene polyol include polyoxytetramethylene polyol, polyoxyethylene polyol, polyoxypropylene polyol, and polyoxyethylene polyoxypropylene polyol.

  Examples of the polyether polyester polyol include polyols obtained by condensation polymerization of ether diols and dibasic acid compounds, polyols obtained by ring-opening copolymerization (particularly random copolymerization) of epoxide compounds and cyclic esters, and the like. Can be illustrated. Examples of ether diols include diethylene glycol, dipropylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, and polyoxyethylene polyoxypropylene glycol. Examples of the dibasic acid compound include phthalic acid, maleic acid, adipic acid, and fumaric acid. Examples of cyclic esters (lactones) include β-propiolactone (carbon number 3), δ-valerolactone (carbon number 5), and ε-caprolactone (carbon number 6). Of these, ε-caprolactone is more preferred. The epoxide compound is as described above.

  Examples of the polyester polyol include polyols obtained by condensation polymerization of low molecular diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the aforementioned dibasic acid compound.

  As said polycarbonate polyol, what is obtained by making the low molecular carbonate compound which consists of alkylene carbonate, dialkyl carbonate, and diaryl carbonate react with a diol compound is preferable. Specific examples include polyhexamethylene carbonate diol, poly (3-methylpentene carbonate) diol, and polypropylene carbonate diol. Moreover, those mixtures or those copolymers may be sufficient.

The number of hydroxyl groups in the polyol compound is preferably 2 to 3. If the number of hydroxyl groups is within this range, it is preferable because the viscosity of the resulting silyl group-containing polymer (S) can be easily kept low.
The average hydroxyl value of the polyol compound is preferably 5 to 225 mgKOH / g, more preferably 7 to 115 mgKOH / g, and particularly preferably 10 to 112 mgKOH / g. If the average hydroxyl value is within this range, it is preferable because the viscosity of the resulting silyl group-containing polymer (S) can be easily kept low.
In particular, when the silyl group-containing polymer (S1) is obtained, the average hydroxyl value of the polyol compound is preferably 5 to 112 mgKOH / g, more preferably 7 to 56 mgKOH / g.
The average hydroxyl value of the polyol compound when obtaining the silyl group-containing polymer (S2) or (S3) is preferably 25 to 225 mgKOH / g, more preferably 30 to 115 mgKOH / g.

[Polyisocyanate compound]
In order to obtain the silyl group-containing polymer (S2) or (S3), a polyurethane prepolymer is used. As the polyisocyanate compound used for the synthesis of the polyurethane prepolymer, known compounds can be used. Specific examples include diisocyanate compounds such as diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, methylene-bis (cyclohexyl isocyanate), isophorone diisocyanate and hexamethylene diisocyanate. These may use only 1 type or may use 2 or more types together. A polyisocyanate compound having a bent chain is preferable because flexibility of the obtained pressure-sensitive adhesive body is improved. Specific examples include tolylene diisocyanate, m-xylylene diisocyanate, and isophorone diisocyanate. Of these, tolylene diisocyanate or isophorone diisocyanate is particularly preferred.

[Polyurethane prepolymer]
The polyurethane prepolymer for obtaining the silyl group-containing polymer (S2) or (S3) is obtained by reacting the polyol compound with a polyisocyanate compound. The terminal of the polyurethane prepolymer is an isocyanate group or a hydroxyl group, and is appropriately selected depending on the method for introducing a hydrolyzable silyl group. That is, it may be an isocyanate group-terminated polyurethane prepolymer or a hydroxyl group-terminated polyurethane prepolymer.
When an isocyanate group-terminated polyurethane prepolymer is obtained when synthesizing a polyurethane prepolymer, the ratio of the polyol compound to be reacted and the polyisocyanate compound is the molar ratio of “NCO group of polyisocyanate compound / OH group of polyol compound”. The isocyanate index defined by a value 100 times the ratio is preferably more than 100 to 200, more preferably 105 to 170. When obtaining a hydroxyl group-terminated polyurethane prepolymer, the ratio of the polyol compound to be reacted and the polyisocyanate compound is preferably 50 to less than 100 and more preferably 50 to 98 in terms of isocyanate index.
The molecular weight of the polyurethane prepolymer is preferably 2,000 to 100,000 in terms of number average molecular weight. More preferably, it is 3,000-80,000.

A catalyst (urethanization reaction catalyst) may be used for the reaction between the polyol compound and the polyisocyanate compound. A known urethanization reaction catalyst is used as the catalyst. Examples of the urethanization reaction catalyst include organic acid salts / organometallic compounds, tertiary amines and the like.
Specific examples of organic acid salts and organometallic compounds include tin catalysts such as dibutyltin dilaurate (DBTDL), bismuth catalysts such as bismuth 2-ethylhexanoate [bismuth tris (2-ethylhexanoate)], zinc naphthenate Examples thereof include zinc catalysts such as cobalt catalysts such as cobalt naphthenate and copper catalysts such as copper 2-ethylhexanoate. Tertiary amines include triethylamine, triethylenediamine, N-methylmorpholine and the like.
The reaction temperature is preferably 40 to 160 ° C, more preferably 80 to 120 ° C.

[Polyurethane polymer]
The polyurethane polymer for obtaining the silyl group-containing polymer (S3) is obtained by subjecting a polyurethane prepolymer to a chain extension reaction using a chain extender. The polyurethane prepolymer used at this time is the same as in the case of the silyl group-containing polymer (S2).
The terminal of the polyurethane polymer is an isocyanate group, a hydroxyl group, or an amino group, and is appropriately selected depending on the method for introducing a hydrolyzable silyl group. That is, it may be an isocyanate group-terminated polyurethane polymer, a hydroxyl group-terminated polyurethane polymer, or an amino group-terminated polyurethane polymer.
The molecular weight of the polyurethane polymer is preferably 4,000 to 500,000 in terms of number average molecular weight. More preferably, it is 8,000-250,000.

[Chain extender]
When an isocyanate group-terminated polyurethane prepolymer is used as the polyurethane prepolymer, low-molecular diols and low-molecular diamines are preferred as the chain extender. Preferred examples of the low molecular diols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Low molecular diamines include aliphatic diamines such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine; piperazine, isophoronediamine, dicyclohexyl And alicyclic diamines such as methane-4,4′-diamine; and aromatic diamines such as tolylenediamine, phenylenediamine, and xylylenediamine.
When a hydroxyl-terminated polyurethane prepolymer is used as the polyurethane prepolymer, a diisocyanate compound is preferred as the chain extender. The diisocyanate compound is the same as that used for the polyurethane prepolymer.

In synthesizing the polyurethane polymer, the ratio of reacting the polyurethane prepolymer with the chain extender is appropriately selected depending on the molecular weight of the polyurethane prepolymer and the molecular weight of the target polyurethane polymer.
When the isocyanate group-terminated polyurethane prepolymer is chain-extended using a low molecular diol as a chain extender, the ratio of the isocyanate group-terminated polyurethane prepolymer and the low-molecular diol has an isocyanate index of more than 100 to 200. Is more preferable, and more than 100 to 150 is more preferable. Within this range, an isocyanate group-terminated polyurethane polymer can be obtained. Moreover, when obtaining a hydroxyl-terminated polyurethane polymer, it is preferable that this isocyanate index is less than 50-100, and 50-98 are more preferable.
The isocyanate index is a value 100 times the value obtained by dividing the amount (mole number) of the isocyanate group (NCO group) by the amount (mole number) of the group (OH group or NH ₂ group) capable of reacting with the isocyanate group. is there.
When the isocyanate group-terminated polyurethane prepolymer is chain extended using a low molecular diamine as a chain extender, the ratio of the polyurethane prepolymer and the low molecular diamine is preferably an isocyanate index of 50 to less than 100, 50-98 is more preferable. Within this range, an amino group-terminated polyurethane polymer is obtained.
Moreover, when obtaining an isocyanate group terminal polyurethane polymer, it is preferable that an isocyanate index is more than 100-200, and more than 100-150 is more preferable.
When a hydroxyl group-terminated polyurethane prepolymer is chain-extended using a diisocyanate compound as a chain extender to obtain an isocyanate group-terminated polyurethane polymer, the ratio of the polyurethane prepolymer to the diisocyanate compound is an isocyanate index of more than 100 to 200. It is preferable that 101-150 is more preferable.
Moreover, when obtaining a hydroxyl-terminated polyurethane polymer, it is preferable that this isocyanate index is less than 50-100, and 50-98 are more preferable.

  A catalyst may be used for the reaction between the polyurethane prepolymer and the chain extender. As the catalyst, the above-mentioned urethanization reaction catalyst is used. The reaction temperature is preferably 40 to 160 ° C, more preferably 80 to 120 ° C.

[Hydrolyzable silyl group]
In the present invention, the hydrolyzable silyl group is a silyl group having a hydrolyzable group. Specifically, a silyl group represented by -SiX _a R ⁰ _(3-a) is preferable. Here, a represents an integer of 1 to 3. a is preferably 2 to 3, and 3 is most preferable.
R ⁰ is a monovalent organic group having 1 to 20 carbon atoms, preferably a monovalent organic group having 1 to 6 carbon atoms. Specific examples include methyl group, ethyl group, propyl group, butyl group, pentyl group and the like. R ⁰ may have a substituent. Examples of the substituent include a methyl group and a phenyl group.
If the hydrolyzable silyl group has a plurality of R ^0, R ⁰ the plurality of it may be the same or different from each other. That is, when a is 1, two R ⁰ bonded to one silicon atom (Si) are each independently a monovalent monovalent group having 1 to 20 carbon atoms that may have a substituent. An organic group is shown.
X represents a hydroxyl group (—OH) or a hydrolyzable group. Examples of the hydrolyzable group include -OR group (R is a hydrocarbon group having 4 or less carbon atoms). Such —OR group is preferably an alkoxy group or an alkenyloxy group, and particularly preferably an alkoxy group.
The number of carbon atoms of the alkoxy group or alkenyloxy group is preferably 4 or less. Specific examples include a methoxy group, an ethoxy group, a propoxy group, and a propenyloxy group. Among these, a methoxy group or an ethoxy group is more preferable. In this case, the reactivity during curing is improved and the curing rate is further increased.
When a plurality of X are present in the hydrolyzable silyl group, the plurality of X may be the same as or different from each other. That is, when a is 2 or 3, each X independently represents a hydroxyl group or a hydrolyzable group.
In particular, as the hydrolyzable silyl group, a trialkoxysilyl group is preferable, since the storage stability of the silyl group-containing polymer (S) is good, the reactivity at the time of curing is excellent, and the curing speed is fast. A trimethoxysilyl group or a triethoxysilyl group is more preferable, and a trimethoxysilyl group is particularly preferable.

[Introduction of hydrolyzable silyl group]
In the present invention, a hydrolyzable silyl group is introduced into the molecular terminal of the polyol compound, polyurethane prepolymer or polyurethane polymer. As a method for introducing a hydrolyzable silyl group, a method using an isocyanate silane (PQ1), a method using an aminosilane (PQ2), a method using a mercaptosilane (PQ3), a method using an epoxysilane (PQ4), And a method (PQ5) using hydrosilanes.
The proportion of the hydrolyzable silyl group introduced into the molecular terminal of the polyol compound, polyurethane prepolymer or polyurethane polymer (hereinafter sometimes referred to as the hydrolyzable silyl group introduction rate) is the theoretically reactive end group. When the total is 100 mol%, 50 to 100 mol% is preferably introduced, and 80 to 100 mol% is more preferably introduced.

  In the case where the silyl group-containing polymer (S) has a urethane bond or a urea bond, the ratio (MU / MS ratio) of the total amount (MU) of the urethane bond and the urea bond and the amount of hydrolyzable silyl group (MS). (Molar ratio) is not particularly limited, but MU / MS (molar ratio) is preferably 1/1 to 100/1. By being in this range, the adhesive force and flexibility of the adhesive body are controlled. Also, the stability of the adhesive force is improved. Urethane bonds are formed by the reaction of isocyanate groups and hydroxyl groups, and urea bonds are formed by the reaction of isocyanate groups and amino groups. In the case of the silyl group-containing polymer (S2) or (S3), the molar ratio of MU / MS can be controlled by the molecular weight of the polyurethane prepolymer or polyurethane polymer.

[Method using isocyanate silanes (PQ1)]
In the method (PQ1), the terminal functional group of the polyol compound, polyurethane prepolymer or polyurethane polymer is a group capable of reacting with an isocyanate group, and hydrolysis is carried out by reacting the terminal functional group with isocyanate silanes. A functional silyl group is introduced.
Isocyanate silanes include isocyanate methyltrimethoxysilane, 2-isocyanatoethyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 4-isocyanatobutyltrimethoxysilane, 5-isocyanatepentyltrimethoxysilane, isocyanatemethyltriethoxysilane, 2-isocyanatoethyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, 4-isocyanatobutyltriethoxysilane, 5-isocyanatepentyltriethoxysilane, isocyanatemethylmethyldimethoxysilane, 2-isocyanateethylethyldimethoxysilane, 3-isocyanate Examples include propyltrimethoxysilane or 3-isocyanatopropyltriethoxysilane It is.
Among these, 3-isocyanatopropyltrimethoxysilane or 3-isocyanatopropyltriethoxysilane is preferable.
Examples of the group capable of reacting with an isocyanate group include a hydroxyl group and an amino group. When a hydroxyl group is used, a polyol compound, a hydroxyl group-terminated polyurethane prepolymer, a hydroxyl group-terminated polyurethane prepolymer, and a hydroxyl group-terminated polyurethane polymer obtained by subjecting a hydroxyl group-terminated polyurethane prepolymer to a chain extension reaction using a diisocyanate compound, A hydroxyl group-terminated polyurethane polymer obtained by reacting diols can be used.
When an amino group is used, an amino group-terminated polyurethane polymer obtained by subjecting an isocyanate group-terminated polyurethane prepolymer to a chain extension reaction using a low-molecular diamine can be used.
A catalyst may be used for this reaction. As the catalyst, the above-mentioned urethanization reaction catalyst is used.

[Method using aminosilanes (PQ2)]
In the method (PQ2), the terminal functional group of the polyol compound, the polyurethane prepolymer or the polyurethane polymer is a group capable of reacting with an amino group, and the hydrolyzability is obtained by reacting the terminal functional group with aminosilanes. A silyl group is introduced. If necessary, a group capable of reacting with an amino group may be introduced at the end of the polyol compound, polyurethane prepolymer or polyurethane polymer.

Examples of aminosilanes include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriisopropoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3- ( 2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropylmethyl Diethoxysilane, 3- (2-aminoethyl) aminopropyltriisopropoxysilane, 3- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane, 3- (6-aminohexyl) aminopropyltri Methoxysila 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, N- (2-aminoethyl) aminomethyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane Ureidopropyltrimethoxysilane, ureidopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenylaminomethyltrimethoxysilane, N-benzyl-3-aminopropyltrimethoxysilane, N-vinylbenzyl -3-aminopropyltriethoxysilane, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxy Chirushiran, N- phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyl trimethoxy silane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine, and the like.
Among these, 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane is preferable.

Examples of the group capable of reacting with an amino group include an isocyanate group, an acryloyl group, and a methacryloyl group. When an isocyanate group is used, an isocyanate group-terminated polyurethane prepolymer and a hydroxyl group-terminated polyurethane prepolymer further obtained by subjecting the diisocyanate compound to a chain extension reaction and an isocyanate group-terminated polyurethane prepolymer are further reduced. For example, an isocyanate group-terminated polyurethane polymer obtained by chain extension reaction using a molecular diol compound can be used.
When an acryloyl group or a methacryloyl group is used, an isocyanate group-terminated polyurethane prepolymer reacted with a hydroxyalkyl acrylate or hydroxyalkyl methacrylate, a polyol compound, a hydroxyl-terminated polyurethane prepolymer or a hydroxyl-terminated polyurethane polymer with acrylic acid Alternatively, a product obtained by reacting methacrylic acid can be used. Examples of hydroxyalkyl acrylates include hydroxyethyl acrylate and hydroxybutyl acrylate. Examples of hydroxyalkyl methacrylates include hydroxyethyl methacrylate and hydroxybutyl methacrylate. The reaction between an amino group and an isocyanate group is a urea bond formation reaction. In this reaction, the above-mentioned urethanization catalyst may be used. The reaction between an amino group and an acryloyl group is a Michael addition reaction.

[Method using mercaptosilanes (PQ3)]
In the method (PQ3), the terminal functional group of a polyol compound, polyurethane prepolymer or polyurethane polymer is a group capable of reacting with a mercapto group, and hydrolysis is carried out by reacting the terminal functional group with mercaptosilanes. A functional silyl group is introduced. If necessary, a group capable of reacting with a mercapto group may be introduced at the end of the polyol compound, polyurethane prepolymer or polyurethane polymer.
Mercaptosilanes include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane. Etc. Among these, 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane is preferable.
Examples of the group capable of reacting with a mercapto group include an isocyanate group, an acryloyl group, and an allyl group. The case of an isocyanate group and an acryloyl group is the same as in the case of the method using aminosilanes (PQ2). When an allyl group is used, the end of the polyurethane prepolymer or polyurethane polymer can be converted to an isocyanate group and then reacted with allyl alcohol to form an allyl group.
The reaction between the mercapto group and the isocyanate group is the same as the urethanization reaction, and a catalyst may be used. The reaction between the mercapto group and the acryloyl group or allyl group is preferably performed using a radical initiator. Examples of the radical initiator include azobisisobutyronitrile (AIBN).

[Method using epoxy silanes (PQ4)]
In the method (PQ4), the terminal functional group of the polyol compound, polyurethane prepolymer or polyurethane polymer is a group capable of reacting with an epoxy group, and by reacting the terminal functional group with epoxy silanes. A hydrolyzable silyl group is introduced. If necessary, a group capable of reacting with an epoxy group may be introduced at the end of the polyol compound, polyurethane prepolymer or polyurethane polymer.
As epoxy silanes, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and the like are preferable. Among these, 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane is preferable.
Examples of the group capable of reacting with the epoxy group include a hydroxyl group and an amino group. Each is the same as in the method (PQ1) using isocyanate silanes. As the catalyst in the reaction with the epoxy group, known ones such as amines and acid anhydrides are used. Examples include chain aliphatic polyamines, alicyclic polyamines, aromatic polyamines, modified aliphatic polyamines, imidazole compounds, and the like. In particular, tertiary amines such as N, N-dimethylpiperazine, triethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30) and benzyldimethylamine (BDMA) are preferable.

[Method using hydrosilanes (PQ5)]
In the method (PQ5), the terminal functional group of the polyol compound, polyurethane prepolymer or polyurethane polymer is a group capable of hydrosilylation reaction, and the hydrolyzable silyl group is reacted with hydrosilanes. Introduce a group. If necessary, a group capable of hydrosilylation reaction may be introduced at the end of the polyol compound, polyurethane prepolymer or polyurethane polymer.
Examples of hydrosilanes include trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldi Examples thereof include siloxane.
Examples of groups capable of undergoing hydrosilylation include acryloyl groups and allyl groups. Each is the same as the method (PQ3) using mercaptosilanes. It is preferable to use a hydrosilylation catalyst for this reaction. Examples of the hydrosilylation catalyst include chloroplatinic acid.

<Curing catalyst (A)>
The curable composition of the present invention includes an iron chelate compound (A1) and a metal compound other than the iron chelate compound (A2) as a curing catalyst for promoting hydrolysis and / or crosslinking reaction of the hydrolyzable silyl group. (In the present specification, the curing catalyst (A) including simply “metal compound (A2)”) is included.

[Iron chelate compound (A1)]
Examples of the iron chelate compound (A1) include tris (acetylacetonato) iron, tris (benzoylacetonato) iron, and tris (acetylacetoacetate) iron. Of these, tris (acetylacetoacetate) iron is more preferable in terms of reactivity and curability.
The iron chelate compound (A1) may be one type or a combination of two or more types.

[Metal Compound (A2)]
As the metal compound (A2), a known metal compound can be appropriately used as a curing catalyst for a polymer having a hydrolyzable silyl group at the molecular end.
The metal compound (A2) includes one or more selected from the group consisting of calcium compounds, vanadium compounds, titanium compounds, potassium compounds, barium compounds, manganese compounds, nickel compounds, cobalt compounds, zirconium compounds, aluminum compounds and bismuth compounds. It is preferable. 50% by mass or more of the metal compound (A2) is preferably at least one selected from the above group, more preferably 80% by mass or more, and most preferably 100% by mass. It is preferable that a titanium compound, a zirconium compound, an aluminum compound or a bismuth compound is included, and a titanium compound is more preferable because it is easy to express reactivity and curability in combination with the metal compound (A1).
As a metal compound (A2), you may use 1 or more types of well-known organotin compounds (for example, dibutyltin dilaurate, dibutyltin diacetonate etc.) as a curing catalyst of the polymer which has a hydrolyzable silyl group. From the viewpoint of environmental burden, it is preferable that the amount of the organotin compound used is small. The proportion of the organotin compound in the metal compound (A2) is preferably 50% by mass or less, more preferably 20% by mass or less, and most preferably zero.
One type of metal compound (A2) may be used, or two or more types may be used in combination.

The metal compound (A2) is preferably (i) a metal salt, (ii) a metal alkoxide, or (iii) a metal chelate compound.
(I) Metal salt The metal salt is preferably a carboxylic acid metal salt. Specifically, Ca (OCOR) ₂ , V (OCOR) ₂ , Ti (OCOR) ₄ , K (OCOR), Ba (OCOR) ₂ , Mn (OCOR) ₂ , Ni (OCOR) ₂ , Co (OCOR) ₂ , Zr (O) (OCOR) ₂ , and Bi (OCOR) ₂ . (OCOR) represents a monovalent residue obtained by removing a hydrogen atom from a carboxylic acid (hereinafter referred to as a carboxylic acid group).
As the carboxylic acid constituting the carboxylic acid metal salt, a hydrocarbon-based carboxylic acid group-containing compound having 2 to 40 carbon atoms including carbonyl carbon is preferable, and a hydrocarbon system having 2 to 20 carbon atoms from the viewpoint of availability. The carboxylic acid group-containing compound is more preferable.

  Specific examples of the carboxylic acid group-containing compound include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecyl Linear saturated fatty acids such as acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, and laccelic acid; undecylenic acid , Lindelic acid, Tuzuic acid, Fizeteric acid, Myristoleic acid, 2-Hexadecenoic acid, 6-Hexadecenoic acid, 7-Hexadecenoic acid, Palmitoleic acid, Petroceric acid, Oleic acid, Elaidic acid, Asclepic acid, Vaxenoic acid, Gadelic acid , Gondoic acid, cetreic acid, erucic acid, Monoene unsaturated fatty acids such as lacidic acid, cerakoleic acid, ximenoic acid, lumenic acid; linoleic acid, 10,12-octadecadienoic acid, hiragoic acid, α-eleostearic acid, β-eleostearic acid, punicic acid , Linolenic acid, 8,11,14-eicosatrienoic acid, 7,10,13-docosatrienoic acid, 4,8,11,14-hexadecatetraenoic acid, moloctic acid, stearidonic acid, arachidonic acid, 8,12 , 16,19-docosatetraenoic acid, 4,8,12,15,18-eicosapentaenoic acid, sardine acid, nisinic acid, docosahexaenoic acid and other polyene unsaturated fatty acids; isoacid, anteisoacid, tuberculostearic acid Branched fatty acids such as pivalic acid, neodecanoic acid; taliphosphoric acid, stearolic acid, crepenic acid, xymenic acid, -Fatty acids having a triple bond such as hexadecynoic acid; alicyclic carboxylic acids such as naphthenic acid, malvalic acid, sterlic acid, hydonocarbic acid, sholmoulinic acid, gorulinic acid; sabinic acid, 2-hydroxytetradecanoic acid, iprolic acid 2-hydroxyhexadecanoic acid, yarapinolic acid, uniperic acid, ambrettelic acid, aleurit acid, 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, ricinoleic acid , Oxygen-containing fatty acids such as camlorenic acid, licanoic acid, ferronic acid and cerebronic acid;

  When the carboxylic acid has a high melting point (high crystallinity), the carboxylic acid metal salt having the carboxylic acid group also has a high melting point, making it difficult to handle (poor workability). Therefore, the melting point of the carboxylic acid is preferably 65 ° C. or less, more preferably −50 to 50 ° C., and particularly preferably −40 to 35 ° C.

When the carbon number of the carboxylic acid is large (the molecular weight is large), the carboxylic acid metal salt having the acid group is in a solid state or a liquid with a high viscosity and is difficult to handle (poor workability). Conversely, when the carbon number of the carboxylic acid is small (molecular weight is small), the carboxylic acid metal salt having the carboxylic acid group contains many components that are easily volatilized by heating, and the catalytic ability of the carboxylic acid metal salt is high. May decrease. In particular, when the curable composition is cured in a thinly stretched (thin layer) state, volatilization due to heating is large, and the catalytic ability of the carboxylic acid metal salt may be greatly reduced.
From these points, the carboxylic acid is preferably a carboxylic acid group-containing compound having 2 to 17 carbon atoms including the carbon of the carbonyl group, more preferably a carboxylic acid group-containing compound having 3 to 13 carbon atoms. 10 is particularly preferred.

  Specific examples of preferred carboxylic acid metal salts from the viewpoints of availability and compatibility include bismuth octylate (divalent), titanium 2-ethylhexanoate (tetravalent), vanadium 2-ethylhexanoate (trivalent), Calcium 2-ethylhexanoate (divalent), potassium 2-ethylhexanoate (monovalent), barium 2-ethylhexanoate (divalent), manganese 2-ethylhexanoate (divalent), nickel 2-ethylhexanoate (Divalent), cobalt 2-ethylhexanoate (divalent), zirconium 2-ethylhexanoate (tetravalent), titanium neodecanoate (tetravalent), vanadium neodecanoate (trivalent), calcium neodecanoate (divalent) , Potassium neodecanoate (monovalent), barium neodecanoate (divalent), zirconium neodecanoate (tetravalent), titanium oleate (tetravalent) Vanadium oleate (trivalent), calcium oleate (divalent), potassium oleate (monovalent), barium oleate (divalent), manganese oleate (divalent), nickel oleate (divalent), oleic acid Cobalt (divalent), zirconium oleate (tetravalent), titanium naphthenate (tetravalent), vanadium naphthenate (trivalent), calcium naphthenate (divalent), potassium naphthenate (monovalent), barium naphthenate ( Divalent), manganese naphthenate (divalent), nickel naphthenate (divalent), cobalt naphthenate (divalent), zirconium naphthenate (tetravalent), and the like.

  From the viewpoint of catalytic activity and curability, bismuth octylate (divalent), titanium 2-ethylhexanoate (tetravalent), calcium 2-ethylhexanoate (divalent), potassium 2-ethylhexanoate (monovalent), Barium 2-ethylhexanoate (divalent), zirconium 2-ethylhexanoate (tetravalent), titanium neodecanoate (tetravalent), calcium neodecanoate (divalent), potassium neodecanoate (monovalent), barium neodecanoate ( Divalent), zirconium neodecanoate (tetravalent), titanium oleate (tetravalent), calcium oleate (divalent), potassium oleate (monovalent), barium oleate (divalent), zirconium oleate (tetravalent) ), Titanium naphthenate (tetravalent), calcium naphthenate (divalent), potassium naphthenate (monovalent), barium naphthenate Divalent), zirconium naphthenate (tetravalent) is more preferable.

As a method for producing a carboxylic acid metal salt, an aqueous solution of sodium soap is prepared by reacting a carboxylic acid group-containing compound or its ester with sodium hydroxide, and an aqueous solution of a metal salt prepared separately is added. Precipitation method for precipitating; a melting method in which a carboxylic acid group-containing compound or its ester and a metal hydroxide, oxide, or weak acid salt are reacted at a high temperature; a direct method in which a carboxylic acid group-containing compound and a metal powder are reacted; A method of reacting an alcoholate or chloride with a carboxylic acid group-containing compound in an organic solvent can be used.
The carboxylic acid metal salt is preferably diluted with a diluent such as mineral spirit, toluene, hexylene glycol, diethylene glycol, white kerosene, dioctyl phthalate, and used in the form of a solution having a metal content of about 1 to 40% by mass.

(Ii) Metal alkoxides As metal alkoxides, titanium alkoxides such as tetraisopropyl titanate, tetrabutyl titanate, tetramethyl titanate, tetra (2-ethylhexyl titanate); aluminum isopropylate, mono-sec-butoxyaluminum di Aluminum alkoxides such as isopropylate; zirconium alkoxides such as zirconium-n-propylate and zirconium-n-butyrate.

(Iii) Metal chelate compounds As chelating agents for metal chelate compounds, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, isopropyl acetoacetate, acetoacetate-n-butyl, acetoacetate-sec-butyl, aceto Β-ketoesters such as tert-butyl acetate; acetylacetone, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane-2,4-dione, nonane-2, Β-diketones such as 4-dione and 5-methyl-hexane-2,4-dione; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc. Saturated aliphatic dicarboxylic acids; glycols such as ethylene glycol; glycolic acids such as oxyacetic acid; ethylenedia Tetraacetic acid (EDTA) and its sodium salt, ethylenediamine, 1,3-propanediamine, diethylenetriamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, tris [2- (dimethylamino) ethyl] amine, tri (pyridinylmethyl) amine, etc. A nitrogen-containing compound of: furan carboxylic acid, thiophene carboxylic acid, nicotinic acid, isonicotinic acid, phenanthroline, diphenanthroline, substituted phenanthroline, 2,2 ′, 6 ′, 2 ″ -terpyridine, pyridineimine, crosslinked aliphatic diamine, 4 , 4′-di (5-nonyl) -2,2′-bipyridine, bipyridine coordinated with O, S, Se, Te, alkyliminopyridine, alkylbipyridinylamine, alkyl-substituted tripyridine, di (alkylamino) Alkylpi Gins, ethylenediaminedipyridine, other heterocyclic compounds; Marcapto alcohols such as 2-mercaptoethanol; Dithiols such as ethanedithiol; Mercaptoamines such as 2-mercaptoethylamine; Dithioketones such as 2,4-pentanedithione And sulfur-containing compounds such as;

Examples of the metal chelate compound include general formulas Zr (OR ¹¹ ) _p (R ¹² COCHCOR ¹³ ) _4-p , Ti (OR ¹¹ ) _q (R ¹² COCHCOR ¹³ ) _4-q and Al (OR ¹¹ ) _r (R ¹² The compound represented by COCHCOR ¹³ ) _3-r is preferred.
In the above general formula, R ¹¹ and R ¹² are each independently an alkyl group having 1 to 6 carbon atoms (ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group). , N-pentyl group, phenyl group and the like. R ¹³ is the same alkyl group having 1 to 6 carbon atoms and alkoxy group having 1 to 16 carbon atoms as described above (methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group). Group, t-butoxy group, lauryl group, stearyl group, etc.). P to q are integers of 0 to 3, and r is an integer of 0 to 2.

Specific examples of metal chelate compounds include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethyl acetoacetate) zirconium, n-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (n-propyl acetoacetate). Zirconium chelate compounds such as zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diisopropoxy Titanium chelate compounds such as bis (acetylacetone) titanium, di-n-butoxy bis (acetylacetate) titanium; diisopropo Siethylacetoacetate aluminum, diisopropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, Examples thereof include aluminum chelate compounds such as monoacetylacetonate and bis (ethylacetoacetate) aluminum.
Of these, preferred are tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetate) titanium, and di-n-butoxybis (Acetyl acetate) titanium is most preferred.

  As the metal compound (A2), (iii) a metal chelate compound is preferable in that it is easy to express reactivity and curability in combination with the metal compound (A1). Among these, a titanium chelate compound, a zirconium chelate compound, or an aluminum chelate compound is more preferable, and a titanium chelate compound is more preferable in that it is easy to express reactivity and curability.

0.001-10 mass parts is preferable with respect to 100 mass parts of silyl group containing polymer (S), and, as for content of the curing catalyst (A) in the curable composition of this invention, 0.01-5 mass parts Is more preferable. By setting the addition amount of the curing catalyst (A) to 0.001 part by mass or more, it is easy to sufficiently improve the reactivity at the time of curing, and a high curing rate is easily obtained. It is easy to ensure pot life by setting it to 10 parts by mass or less.
The ratio of the iron chelate compound (A1) and the metal compound (A2) in the curing catalyst (A) is preferably a mass ratio (A1) / (A2) = 0.01 / 1 to 10/1, and 0.05 / 1. ~ 5/1 is more preferred. When the ratio of the iron chelate compound (A1) is 0.01 or more and 10 or less with respect to 1 of the metal compound (A2), the curing rate can be adjusted within a sufficient pot life, and the cured state including internal curing Tends to be good.

<Additives>
The curable composition of the present invention may contain additives in addition to the curing catalyst (A).
Known additives can be used as appropriate. Examples thereof include a curing agent, a dehydrating agent, a base material throwing power improver (P), a stabilizer, a flame retardant, an antistatic agent, and a mold release agent described below.
The curable composition of the present invention has a low viscosity and can be applied without a solvent, but may contain a solvent.
In the curable composition of the present invention, it is preferable not to use a plasticizer. In particular, it is preferable not to use an ester plasticizer such as dioctyl phthalate. If ester plasticizers are used, the adhesive strength between the cured product (adhesive) and the substrate such as a film that is peeled off integrally with this may decrease, and adhesive deposits may occur. It is.

[Curing agent]
The curable composition containing the silyl group-containing polymer (S) is cured by contact with water. Therefore, it reacts with water in the atmosphere and is cured by moisture. Also, just prior to curing, water (H 2 _O) may be added as a curing agent. The amount of water added in this case is the silyl group-containing polymers (S1) to (S3), other hydrolyzable silyl group-containing polymers and hydrolyzable silyl group-containing base anchoring force improvers (P). It is preferable that it is 0.01-5 mass parts with respect to 100 mass parts of total amount of, 0.01-1 mass part is more preferable, 0.05-0.5 mass part is especially preferable. Curing can be effectively promoted by setting the addition amount of the curing agent to 0.01 parts by mass or more, and if the addition amount of the curing agent is 5 parts by mass or less, the pot life can be easily secured.

[Dehydrating agent]
In order to improve the storage stability, the curable composition may contain a small amount of a dehydrating agent as long as the effects of the present invention are not impaired.
Specific examples of such dehydrating agents include alkyl orthoformate such as methyl orthoformate and ethyl orthoformate; alkyl orthoacetate such as methyl orthoacetate and ethyl orthoacetate; methyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane or tetra Examples include hydrolyzable organic silicone compounds such as ethoxysilane; hydrolyzable organic titanium compounds and the like. Among these, vinyltrimethoxysilane or tetraethoxysilane is preferable from the viewpoints of cost and dehydration ability.
When adding a dehydrating agent to a curable composition, the addition amount is silyl group containing polymer (S1)-(S3), the polymer which has another hydrolyzable silyl group, and a base material throwing power improvement agent (P ) Is preferably 0.001 to 30 parts by mass, and more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount.

[Base material anchoring force improver (P)]
The curable composition may contain a base material anchoring force improver. The base material anchoring force improver (P) is an additive that improves the adhesive force between the pressure-sensitive adhesive layer and the base material.
As the substrate anchoring force improver (P), it is preferable to use one or more selected from the group consisting of a silane coupling agent, an isocyanate compound, and a urethane resin. In particular, the use of a silane coupling agent is particularly preferred because the adhesive strength to the base material is improved by addition of a relatively small amount and at the same time there is almost no bleeding out from the pressure-sensitive adhesive.
As the silane coupling agent, a silane coupling agent having a hydrolyzable group is preferable. Specific examples of the silane coupling agent having a hydrolyzable group include isocyanate silanes, aminosilanes, mercaptosilanes, and epoxysilanes, and aminosilanes and epoxysilanes are particularly preferable. Preferred examples of these silanes include the compounds specifically exemplified in the aforementioned methods (PQ1) to (PQ4) for introducing hydrolyzable silyl groups.

As the isocyanate compound as the base material anchoring force improver (P), a polyfunctional polyisocyanate such as a modified product of a known polyisocyanate compound can be suitably exemplified. Examples of the modified body include a trimethylolpropane adduct-type modified body, a burette-type modified body, and an isocyanurate-type modified body. Specifically, Duranate P301-75E (manufactured by Asahi Kasei Co., Ltd., trimethylolpropane adduct type HDI (hexamethylene diisocyanate), isocyanate group content: 12.9 mass%, solid content: 75 mass%), Coronate L (Nippon Polyurethane Co., Ltd.) And trimethylolpropane adduct type TDI (tolylene diisocyanate), isocyanate group content: 13.5% by mass, solid content: 75% by mass) and the like.
As the urethane resin as the base material anchoring force improver (P), an isocyanate group-terminated urethane prepolymer and a hydroxyl group-terminated urethane prepolymer can be used. Examples of the hydroxyl-terminated urethane prepolymer include MP2000 (manufactured by Cemedine).
When the base material anchoring force improver (P) is used, the amount added is 100 parts by mass of the total amount of the silyl group-containing polymers (S1) to (S3) and other hydrolyzable silyl group-containing polymers. On the other hand, 0.01-10 mass parts is preferable, and 0.01-6 mass parts is more preferable. Adhesive residue is suppressed as it is 0.01 mass part or more and 10 mass parts or less.

[Other additives]
You may mix | blend the following stabilizer, a flame retardant, an antistatic agent, or a mold release agent etc. with a curable composition.
Examples of the stabilizer include an antioxidant, an ultraviolet absorber, and a light stabilizer.
Examples of the flame retardant include chloroalkyl phosphate, dimethylmethylphosphonate, ammonium polyphosphate, or an organic bromine compound.
Examples of the antistatic agent include polymer surfactants, inorganic salts, ionic fluids, and the like.
Examples of the mold release agent include wax, soaps, or silicone oil.

[solvent]
The solvent is not particularly limited. For example, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers, ester alcohols, ketone alcohols, ether alcohols , Ketone ethers, ketone esters or ester ethers.
Among these, it is preferable to use alcohols as the solvent because the storage stability of the curable composition can be improved. The alcohol is preferably an alkyl alcohol having 1 to 10 carbon atoms, more preferably methanol, ethanol, isopropyl alcohol, isopentyl alcohol or hexyl alcohol, and further preferably methanol or ethanol. In particular, when methanol is used, if the amount added is increased, the pot life of the curable composition can be extended. That is, this is an effective technique for prolonging the time required to reach a predetermined viscosity after preparation of the curable composition, so-called pot life.
When adding a solvent to the 1st, 2nd curable composition, the addition amount is silyl group containing polymer (S1)-(S3), the polymer which has another hydrolyzable silyl group, and a base material investment. It is preferably 500 parts by mass or less, and more preferably 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the force improver (P). When the addition amount exceeds 500 parts by mass, the cured product may shrink as the solvent volatilizes.

<Adhesive>
The pressure-sensitive adhesive body of the present invention is obtained by curing the curable composition of the present invention. It is also possible to mold after curing of the curable composition. For example, the curable composition can be cured into an appropriate shape such as a sheet and then molded into a predetermined shape by performing die cutting or the like, and used alone as an adhesive. However, it is preferable to apply the curable composition to a substrate and cure it to use as a laminate.
The curing conditions for the curable composition are set as necessary. It is preferable to have the process of heating and hardening a curable composition. For example, after adding and mixing a predetermined amount of water as a hardening | curing agent as needed, a curable composition is coated on a base material. The coating thickness is appropriately set. Thereafter, the curable composition can be cured by heating in an oven or the like and curing at room temperature as necessary. It is also effective to leave it in a humidified environment when curing at room temperature or after curing. Although heating with respect to a curable composition is based also on the heat-resistant temperature etc. of a base material, 60-150 degreeC is preferable and 80-120 degreeC is more preferable. The time for maintaining the heating temperature (heating time) is preferably 0.5 to 30 minutes, and preferably about 1 to 5 minutes. In particular, when a solvent is used, it is preferable to set the heating time so that the solvent is dried. However, rapid drying is not preferable because it causes foaming. Steam may also be applied in or after removal from the oven.

  Application of the curable composition can also be performed continuously. That is, the curable composition is applied to the substrate taken out from the roll, and is heated and dried in an in-line oven. A separator is combined with the obtained molded body (laminated body) as necessary, and wound. A pressure-sensitive adhesive body formed by storing and curing in a room temperature environment humidified as necessary is obtained. As another coating method, the substrate and the separator may be reversed in the above method. That is, it may be coated on the separator first, and the substrate may be attached later.

<Adhesive laminate (adhesive sheet)>
The present invention provides an adhesive laminate (hereinafter sometimes simply referred to as a laminate) having at least one base material layer and an adhesive layer made of the adhesive of the present invention. When the laminate is in the form of a sheet, the laminate becomes an adhesive sheet. An adhesive tape can be obtained by molding the laminate into a tape shape.
In addition, when a curable composition is applied to a separator without using a base material and cured to obtain a cured body, and then the separator is peeled off, it is possible to handle the adhesive body alone. In this case, for example, a double-sided pressure-sensitive adhesive sheet is obtained. The curable composition of the present invention has a low viscosity and excellent coating properties even when no solvent is used. For this reason, favorable coating is possible also to a separator.
Specifically, by applying a curable composition to a separator, drying by heating, laminating another separator, and curing, a pressure-sensitive adhesive sheet only having no base material is obtained. can get. At this time, without using another separator, the back surface of the separator coated first may be wound to produce a roll of an adhesive.

The laminated body may have another layer as needed. For example, an adhesive layer (including a primer layer) may be provided between the base material layer and the pressure-sensitive adhesive layer to prevent peeling of the base material and the pressure-sensitive adhesive body. Moreover, you may provide the buffer body layer which consists of a foam etc. between a base material layer and an adhesive body layer. Further, a conductive material layer may be provided between the base material layer and the adhesive layer. The conductive material layer is obtained by applying a conductive material such as a metal-based conductive material, an ionic conductive material, or a carbon-based conductive material to the base material layer. The conductive material may be applied alone or in combination with a binder such as various resins. Moreover, you may provide a separator (release liner) layer on the opposite side to the base material layer of an adhesion body layer. Moreover, you may provide a printing layer in the opposite side to the adhesion body layer of a base material layer. When a printing layer is provided, printing can be performed and design properties can be enhanced. Moreover, you may provide an adhesive body layer on both surfaces on both sides of a base material layer.
In this case, a double-sided pressure-sensitive adhesive sheet or the like is obtained.

<Base material>
The material of the substrate is not particularly limited. Preferred examples include polyesters such as polyethylene terephthalate (PET); polyolefins such as polyethylene, polypropylene, and polyethylene-polypropylene copolymers (block copolymers and random copolymers); halogenated polyolefins such as polyvinyl chloride; Examples include paper such as cardboard; cloth such as woven fabric and nonwoven fabric; metal foil such as aluminum foil. These base materials may be used in combination. For example, you may use the laminated body which laminated | stacked the PET layer, the metal foil layer, and the polyethylene layer.
The surface of the substrate may not be processed in advance. In particular, the joint surface with the pressure-sensitive adhesive layer of polyesters and papers is difficult to peel off due to the adhesive effect accompanying the curing of the curable composition without prior processing. If necessary, easy adhesion treatment such as primer treatment may be performed.
On the other hand, when polyolefins are used for the base material, it is preferable that the surface on which the curable composition is applied is subjected to an easy adhesion treatment in advance. This is because the peel adhesive strength may be lowered on an untreated surface. Examples of such easy adhesion treatment include corona treatment (corona discharge treatment) and primer treatment. In particular, the corona treatment is preferable because the treatment is simple and the process can be simplified.
For example, a corona treatment is performed on one side of a polypropylene film having a thickness of 100 μm, and a curable composition is applied to the treated surface. Heat and dry after coating. The film thus obtained can be used as a separator as it is on the surface (back surface) on which no adhesive is provided. That is, an adhesive film can be manufactured by winding this film as it is. That is, it can be wound into a roll without interposing a separator.

<Adhesive layer>
In the pressure-sensitive adhesive sheet or the like of the present invention, the thickness of the pressure-sensitive adhesive layer is not particularly limited. For example, from the point of coating accuracy, 5 μm or more is preferable, and 15 μm or more is more preferable. Moreover, from the point of stability of adhesive force and economical efficiency, 200 μm or less is preferable, 100 μm or less is more preferable, and 80 μm or less is more preferable.

<Separator>
You may affix a separator to the adhesion surface (surface to which a to-be-adhered body is stuck) of said adhesive body layer.
As the separator, in addition to papers subjected to surface treatment with a general release agent, the above-mentioned untreated polyolefins can be used. Moreover, what laminated | stacked polyolefins on base materials, such as paper, can also be used. Silicone oil contained in a conventional separator causes contamination of electronic components. However, when polyolefins are used in the separator, contamination with silicone oil or the like can be prevented. This is useful when the adhesive sheet is applied as a protective sheet for electronic parts and the like. In addition, when polyolefins are used alone as separators, waste can be easily recycled.

<Use of adhesive sheet>
According to the present invention, in particular, a pressure-sensitive adhesive sheet having good wettability and adhesion to an adherend and having low adhesive force and excellent removability can be obtained. In addition, a pressure-sensitive adhesive sheet in which the peel charge amount is suppressed and the high-speed peel property is excellent can be obtained. Accordingly, the application of the pressure-sensitive adhesive sheet specifically includes a protective sheet for electronic materials such as an electronic substrate and an IC chip; a protective sheet for optical members such as a polarizing plate, a light diffusing plate, a light diffusing sheet, and a prism sheet; Protective sheets for automobiles; protective sheets for automobiles; surface protective films for building boards; decorative sheets for wall coverings; surface protection of products such as metal plates, painted steel plates, synthetic resin plates, decorative plywood, heat reflecting glass, etc. . In the case of a relatively large protective sheet such as a protective sheet for automobiles or a temporary fixing application, there may be a case where a certain adhesive force of a low adhesive region is required so as not to be peeled off by wind or the like. The surface protection film for building boards is used for protection during construction and is removed after the interior finishes.
For surface protection applications of products such as metal plates, painted steel plates, synthetic resin plates, decorative plywood, and heat-reflective glass, make sure that there is no dust adhesion or scratches, and that the surfaces of various adherends are contaminated with adhesives after use. It is required to be easily removed.

The protective sheet and the protective tape are peeled and removed when the temporary fixing of the parts and the role of protection are completed. However, when the protective sheet is peeled off from the attached member, static electricity (so-called peeling charge) is generated between the protective sheet and the component. There is a problem that this static electricity has an adverse effect on the circuit of the electronic component, and dust and dirt easily adhere to the surface of the member due to the static electricity. Further, the surface protective film of the liquid crystal display (LCD) is also peeled off during use. When the protective film is peeled from the liquid crystal display, peeling charging may occur.
This peeling electrification may disturb the liquid crystal alignment and disturb the image.
Therefore, in the pressure-sensitive adhesive sheet that is peeled off after sticking, it is required to suppress the generation of static electricity due to peeling charging and to promptly remove the generated static electricity. This is because the surface charge of the adherend causes adhesion of foreign matter and dust to the adherend or causes the function of the adherend to deteriorate.

Moreover, it is preferable that surface protection sheets, such as electronic parts, such as a display, a polarizing plate, an electronic substrate, and an IC chip, can be peeled smoothly at high speed. In general, the tensile force (peeling strength) necessary for peeling an adhesive sheet tends to increase as the tensile speed (peeling speed) increases. However, it is required that the peel strength when peeling at high speed does not increase compared to the peel strength when peeling at low speed. That is, the protective sheet is required to have a low peel rate dependency of the peel strength and to have excellent high speed peel characteristics.
The pressure-sensitive adhesive sheet of the present invention can satisfy such requirements, and in particular, the pressure-sensitive adhesive sheet of the present invention is suitable as a protective sheet that is peeled off during the manufacturing process, such as a protective sheet for electronic materials and a protective sheet for optical members. It is. This is because the adhesive strength is low and the re-peelability is good, the peel charge amount is small, and the high-speed peel property is excellent.

The pressure-sensitive adhesive body of the present invention is excellent in flexibility and wettability. For this reason, even if unevenness exists on the surface of the adherend, good adhesion is ensured. Therefore, it is suitable as an adhesive sheet for protecting an optical member. In addition, the pressure-sensitive adhesive sheet of the present invention has excellent adhesion and can be easily peeled off with a low peel strength even though there is almost no deviation within the sticking surface of the stuck adherend. It is useful for improving the productivity of the manufacturing process.
That is, the pressure-sensitive adhesive sheet of the present invention is suitable as a protective film for a light diffusing plate or a prism sheet, particularly as a protective film for the uneven surface. In addition, since the optical member having the adhesive sheet of the present invention attached thereto has a small change with time in the adhesive strength of the adhesive, it can be peeled with a low peel adhesive strength even after long-term storage, and the peel adhesive strength thereof. Hardly changed. For this reason, the optical member can be stored for a long period of time.

The pressure-sensitive adhesive sheet of the present invention is also suitable as a back grind tape. The back grind tape is a tape that protects the wafer surface during back grind (grinding of the back surface of the wafer) after an electronic circuit is formed on the semiconductor wafer. A back grind tape can be attached to the circuit surface to prevent damage to the circuit surface and contamination of the wafer surface due to the ingress of grinding water and grinding debris.
Moreover, the pressure-sensitive adhesive sheet of the present invention is excellent in adhesion and has a low peel adhesive strength and can be easily peeled off from the adherend. When polyolefins are used as the base material, a separator is unnecessary and contamination such as silicone does not occur. Moreover, since peeling electrification is suppressed, there is little risk of damaging the circuit.

According to the present invention, as a curing catalyst (A), a metal compound (A2) other than the iron chelate compound (A1) and the iron chelate compound is added to the curable composition containing the silyl group-containing polymer (S) as a curing component. By using together, the reactivity at the time of hardening improves favorably, while a hardening rate increases favorably, a favorable hardening state is obtained. That is, the curability is good. The pot life of the curable composition is also long. The cured product has no tack on the surface, and the cured state of the surface and the inside is good and exhibits good removability. Therefore, it is suitable as an adhesive.
The reason why such an effect is obtained is not clear, but as shown in the results of Examples and Comparative Examples described later, the iron chelate compound (A1) has a long pot life and a high curing reaction rate during heating. By using this, curing on the surface of the cured product is accelerated particularly during heating.
Furthermore, the internal curability of the cured product is improved by using the metal compound (A2) in combination. Therefore, by using the iron chelate compound (A1) and the metal compound (A2) other than the iron chelate compound in combination, a cured product (adhesive layer) having a long usable time and a good surface and internal cured state can be obtained. it is conceivable that.

  According to the curable composition of the present invention, it is possible to obtain the same curability as when an organic tin compound is used as a curing catalyst without using a conventional organotin compound, and the pot life is organotin. This can be longer than when a compound is used. In the present invention, an organotin compound can be used in combination. In this case, the amount of the organotin compound used can be reduced without lowering the curability, which is environmentally preferable.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.
In the following, propylene oxide is abbreviated as PO and dibutyltin dilaurate is abbreviated as DBTDL. Pure water was used as the water.

(Reference Production Example 1: Production of double metal cyanide complex catalyst)
Zinc hexacyanocobaltate (hereinafter referred to as TBA-DMC catalyst) having tert-butyl alcohol as an organic ligand was produced by the following method. The polyol X in this example is a polyol having a number average molecular weight (Mn ₁ ) of 1000, obtained by addition polymerization of propylene oxide to dipropylene glycol.
First, an aqueous solution consisting of 10.2 g of zinc chloride and 10 g of water was put into a 500 ml flask, and 4.2 g of potassium hexacyanocobaltate (K ₃₎ was added thereto while stirring at 300 rpm while keeping the aqueous solution at 40 ° C. An aqueous solution consisting of [Co (CN)] ₆ ) and 75 g of water was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred for 30 minutes, and then 40 g of ethylene glycol mono-tert-butyl ether (hereinafter abbreviated as EGMTBE), 40 g of tert-butyl alcohol (hereinafter abbreviated as TBA), 80 g of water, And a mixture of 0.6 g of polyol X were added to the mixture and stirred at 40 ° C. for 30 minutes and further at 60 ° C. for 60 minutes. The obtained reaction mixture was filtered under pressure (0.25 MPa) using a circular filter plate having a diameter of 125 mm and a quantitative filter paper for fine particles (ADVANTEC No. 5C) for 50 minutes to obtain a solid ( The cake containing the double metal cyanide complex) was isolated.

Next, a mixture comprising 18 g of EGMTBE, 18 g of TBA, and 84 g of water was added to the cake containing the double metal cyanide complex and stirred for 30 minutes, followed by pressure filtration (filtration time: 15 minutes). It was. To the cake containing the double metal cyanide complex obtained by filtration, a mixture of 54 g EGMTBE, 54 g TBA, and 12 g water was added and stirred for 30 minutes, and the double metal cyanide having an organic ligand was stirred. A slurry of EGMTBE / TBA containing the complex was obtained.
About 5 g of this slurry was weighed into a flask, dried roughly with a nitrogen stream, and then dried under reduced pressure at 80 ° C. for 4 hours. As a result of weighing the obtained solid, it was found that the concentration of the double metal cyanide complex contained in the slurry was 4.70% by mass.

(Production Example: Production of Polyether-Based Silyl Group-Containing Polymer (S1-1))
[First step]
Using 295 g of Mn = 1000 triol obtained by ring-opening polymerization of PO on glycerin as an initiator, 4130 g of PO was polymerized in the presence of a double metal cyanide complex catalyst to obtain an average hydroxyl value of 11.2 mgKOH / g. Of polyoxypropylene polyol (Mn = 15000, hereinafter referred to as polyol Y) was obtained.

[Second step]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 1000 g of polyol Y obtained above and TMS (3-isocyanatopropyltrimethoxysilane, isocyanate group as isocyanate silanes) Content of 17.87) was added, and DBTDL was added as a urethanization catalyst. The amount of DBTDL used was an amount corresponding to 50 ppm with respect to the total amount of polyol Y and TMS. And it heated up gradually to 80 degreeC, and it reacted until the NCO peak disappeared by IR, and obtained the silyl group containing polymer (S1-1). The hydrolyzable silyl group introduction ratio with respect to the total hydroxyl groups of polyol Y was 97%.

(Examples 1-4 and Comparative Examples 1-7)
[Preparation of curable composition]
In the formulations shown in Tables 1 and 2, a curable composition was prepared by mixing silyl group-containing polymer (S1-1) obtained above, the following curing catalyst (A), and methanol as a solvent. The unit of the blending amount in the table is “part by mass” unless otherwise specified.
[Curing catalyst (A)]
Iron chelate compound A1-1: Iron trisacetylacetonate (manufactured by Nippon Kagaku Sangyo Co., Ltd., product name: nasem ferric iron).
Titanium compound A2-1: dibutoxytitanium bisacetylacetonate (manufactured by Nippon Kagaku Sangyo Co., Ltd., product name: nasem titanium).
Organotin compound A2-2: Dibutyltin bisacetylacetonate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-220).
Zirconium compound A2-3: Tetrakis (acetylacetoacetate) zirconium (manufactured by Nippon Kagaku Sangyo Co., Ltd., product name: nursem zirconium).

[Manufacture of adhesives and adhesive sheets]
As the substrate, a PET film having a thickness of 38 μm subjected to easy adhesion treatment was used.
The curable composition obtained above was coated on the surface of the substrate for easy adhesion so that the film thickness after drying was 15 μm, and then heated at 100 ° C. for 1 minute in a circulation oven. The curable composition was cured by storing for 168 hours in an atmosphere at a temperature of 65 ° C. and a relative humidity of 65% to form an adhesive layer. Thus, an adhesive sheet having an adhesive layer on the substrate was obtained.

(Evaluation methods)
The pot life, curability, and peel strength of the pressure-sensitive adhesive layer of the curable composition were evaluated by the following methods. The results are shown in Tables 1 and 2.
[Pot life]
The curable composition obtained by mixing the silyl group-containing polymer (S1-1), the curing catalyst (A), and the solvent is stored in an atmosphere of 23 ° C. and a relative humidity of 65%, and every hour. A test for coating on a substrate was performed. From the time immediately after mixing until the time when a streak was observed in the coating film when applied or the time until gelation was seen in the curable composition, whichever was earlier, was determined as the pot life.

[Curing property]
The pressure-sensitive adhesive layer heated at 100 ° C. for 1 minute in the above circulating oven was cured for 168 hours in an atmosphere of 23 ° C. and 65% relative humidity, and then the surface of the pressure-sensitive adhesive layer was touched with a finger. ◯ indicates that no mark remains, Δ indicates that there is a tuck but no fingerprint mark, and X indicates that there is a tack and a fingerprint mark remains.

[Peel strength]
As the adherend, a glass plate or a stainless steel plate (thickness: 1.5 mm) made of a SUS-304 alloy specified in JIS and subjected to bright annealing treatment (described as SUS-BA in the table) was used. . The bright annealed surface of this stainless steel plate is almost smooth and glossy.
The pressure-sensitive adhesive layer of the test piece (width: 25 mm) made of the pressure-sensitive adhesive sheet obtained above was attached to an adherend in an atmosphere at 23 ° C., and pressure-bonded with a 2 kg rubber roll. After 30 minutes, 24 hours (1 day), 168 hours (7 days), 336 hours (14 days), and 672 hours (28 days), respectively, a tensile tester specified by JIS B 7721 (manufactured by Orientec, RTE-1210) was used to measure peel strength (180 degree peel, tensile speed 300 mm / min). Tables 1 and 2 show the measured values (unit: N / 25 mm). “C” in the table indicates that there is a portion where cohesive failure occurs due to insufficient internal curing of the pressure-sensitive adhesive layer.
In addition, when sclerosis | hardenability evaluation is (triangle | delta) or x, peeling strength is not measured.

  As shown in the results of Table 1, the curable compositions of Examples 1 to 4 in which the iron chelate compound (A1) and the titanium compound or zirconium compound (A2) are used in combination as a curing catalyst have a high curing reaction rate by heating. At 100 ° C. for 1 minute, a good cured state with no tack and no fingerprint marks was obtained. In addition, the pot life was as good as 6 hours or longer. Furthermore, the pressure-sensitive adhesive layer obtained by curing the curable compositions of Examples 1 to 4 also had a good internal cured state and exhibited good removability, that is, good adhesiveness.

On the other hand, as shown in Table 2, Comparative Example 1 using an organotin compound alone as a curing catalyst had a fast curing rate and good surface and internal curing conditions, but the pot life Was short.
Comparative Examples 2 to 4 and Comparative Example 7 are examples in which the iron chelate compound (A1) was not used and the titanium compound (A2-1) was used alone, but the addition amount of the titanium compound (A2-1) was 1. In Comparative Examples 2, 3, and 7 having a mass part or less, sufficient curability was not obtained. In Comparative Example 4, if the amount is increased to 1.2 parts by mass, the curability is improved, but this is not preferable in terms of cost.
Comparative Examples 5 and 6 are examples in which the iron chelate compound (A1-1) was used alone, but in Comparative Example 5 in which the addition amount of the iron chelate compound (A1-1) was 0.1 parts by mass, The surface of the body layer was tacky and fingerprint marks remained, and the curability was not good. In Comparative Example 6 in which 0.3 part by mass was added, surface tack and fingerprint marks were improved, but because of insufficient internal curability, cohesive failure occurred during the peel test, and re-peelability was not good.

Claims (8)

  The main chain contains a silyl group-containing polymer (S) having a polyether chain, a polyester chain, and / or a polycarbonate chain and a hydrolyzable silyl group at the molecular end, and a curing catalyst (A), and the curing A curable composition characterized in that the catalyst (A) contains an iron chelate compound (A1) and a metal compound (A2) other than the iron chelate compound.   The metal compound (A2) is one or more selected from the group consisting of calcium compounds, vanadium compounds, titanium compounds, potassium compounds, barium compounds, manganese compounds, nickel compounds, cobalt compounds, zirconium compounds, aluminum compounds and bismuth compounds. The curable composition according to claim 1 comprising.   The curable composition according to claim 1 or 2, comprising 0.001 to 10 parts by mass of the curing catalyst (A) with respect to 100 parts by mass of the silyl group-containing polymer (S).   The use ratio of the iron chelate compound (A1) and the metal compound (A2) is 0.01 / 1 to 10/1 in terms of mass ratio (A1) / (A2). The curable composition according to item.   The curable composition according to any one of claims 1 to 4, wherein the hydrolyzable silyl group is a trialkoxysilyl group.   The adhesive body formed by hardening | curing the curable composition as described in any one of Claims 1-5.   A pressure-sensitive adhesive laminate having a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive body according to claim 6 on a substrate.   The manufacturing method of the adhesive body which has the process of heating and hardening the curable composition as described in any one of Claims 1-5.