JP5789087B2 - Non-organotin adhesive composition for interior and cured product thereof - Google Patents

Description

  The present invention includes an interior containing an organic polymer having a hydrolyzable group bonded to a silicon atom and having a silicon group that can be cross-linked by forming a siloxane bond (hereinafter also referred to as “reactive silicon group”). The present invention relates to an adhesive composition.

  An organic polymer having at least one reactive silicon group in the molecule is crosslinked at room temperature by forming a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group by moisture, and a rubber-like cured product is obtained. It is known to have the property of being

  Among organic polymers having a reactive silicon group, polyoxyalkylene polymers and polyisobutylene polymers having a main chain skeleton are disclosed in Patent Document 1 and Patent Document 2, and are already industrially produced. And widely used in applications such as sealing materials, adhesives, and paints. These organic polymers generally have a methyldimethoxysilyl group or a trimethoxysilyl group as a reactive silicon group, and methanol is released into the atmosphere by a hydrolysis reaction. However, it is expected that in the future, it will be required to use a safer organic polymer that does not release methanol than such a demethanol-type organic polymer, particularly for adhesives for interior use.

  On the other hand, a curable composition containing an organic polymer having a reactive silicon group uses a curing catalyst to obtain a cured product. As the curing catalyst, organotin catalysts having a carbon-tin bond, such as dibutyltin bis (acetylacetonate) and dibutyltin dilaurate, are widely used. Recently, however, the toxicity of organotin catalysts has been pointed out. The development of non-organotin catalysts is underway. However, a curable composition prepared using a non-organotin catalyst has poor physical properties such as curability, storage stability, and adhesiveness compared to a curable composition prepared using an organotin catalyst. There were a lot of cases.

  Patent Document 3 and Patent Document 4 disclose a deacetone-type organic polymer having an isopropenoxysilyl group, and further disclose a technique of using an amine compound as a curing catalyst for the deacetone-type organic polymer. Yes. However, when a one-component adhesive composition is prepared using a deacetone-type organic polymer and an amine compound, the curability immediately after the preparation is good, but the viscosity of the adhesive increases after storage for a certain period of time, In severe cases, it hardened in the container and could not be used. Adhesives are not always used immediately after manufacture, but should be stored for several months in warehouses or stores. Curability and viscosity are constant before and after storage (good storage stability) Is desired).

  In the Example of patent document 5, the curable composition produced using the deethanol-type organic polymer which has an ethoxysilyl group, and a titanium catalyst is disclosed. In order to ensure adhesiveness, it is essential for this curable composition to use an organic polymer that gives a cured product having a low tensile stress, that is, a soft (low hardness). However, when an adhesive composition is prepared using such an organic polymer and the base material is bonded to the base material, the adhesive is good, but the cured adhesive is soft. There was a problem of causing a shift between materials. In general adhesives, in order to prevent displacement between substrates to be bonded, it is desired that the cured adhesive has a large tensile stress and is relatively hard (high hardness). Further, it has been found that the deethanol-type organic polymer has a milder hydrolysis reaction than the demethanol-type organic polymer. Therefore, when an adhesive composition is produced using a deethanol-type organic polymer and a non-organotin-based catalyst, it may be particularly difficult to ensure curability that can be practically used.

  In this way, in interior adhesives where safety is required, practicality is used for all of curability, storage stability, adhesiveness, tensile stress, and hardness without using a methanol-free organic polymer or organotin catalyst. The development of adhesives that satisfy the properties is a difficult task and has not yet been accomplished.

JP-A-52-73998 JP-A 63-6041 Japanese Patent Laid-Open No. 7-216216 JP 2010-24369 A WO2005 / 108500 gazette

  The present invention is an adhesive composition for interior use, which includes an organic polymer having a reactive silicon group and a curing catalyst, and is curable, storage stability, adhesiveness, tensile stress, hardness while ensuring safety. An object of the present invention is to provide an excellent adhesive composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an organic polymer (A) having a reactive silicon group having a specific structure without using a demethanol-type organic polymer or an organic tin-based catalyst. And using a titanium catalyst (B), it is found that an interior adhesive composition excellent in curability, storage stability, adhesiveness, tensile stress, and hardness can be obtained while ensuring safety. Completed the invention.

That is, the present invention
(I). (A) An organic polymer having a silicon-containing group that can be crosslinked by forming a siloxane bond, wherein the silicon-containing group has the general formula (1):
-SiR ¹ _3-a X _a (1)
((3-a) pieces of R ¹ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and —OSi (R ² ). ₃ (R ² each independently represents a hydrocarbon group having 1 to 20 carbon atoms) is at least one selected from the group consisting of a triorganosiloxy group, and a number of X is each Independently selected from the group consisting of ethoxy group, isopropoxy group, isopropenoxy group, and acetoxy group, a is an integer of 1 to 3).
(B) a titanium catalyst,
A non-organic tin adhesive composition for interior use, comprising:
(II). The silicon group of component (A) is represented by the general formula (2):
-SiX ₃ (2)
(X is the same as the above), and a non-organotin-based adhesive composition for interior use according to (I),
(III). (A) The main chain skeleton of the component is at least one selected from the group consisting of a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylate polymer, (I) Or the non-organotin adhesive composition for interior use according to (II),
(IV). The non-organotin adhesive composition for interior use according to (III), wherein the polyoxyalkylene polymer is a polyoxypropylene polymer,
(V). The titanium catalyst (B) has the general formula (3):
Ti (OR ³ ) ₄ (3)
(R ³ is an organic group, and four R ^{3 s} may be the same or different from each other.) And / or the general formula (4):
O = Ti (OR ³ ) ₂ (4)
(R ³ are the same. Above) a titanium catalyst represented by, (I) ~ non-organotin adhesive composition for interior according to any one of (IV),
(VI). The titanium catalyst has the general formula (5):

(B R ^{4 's} are each independently a hydrocarbon group having 1 to 20 carbon atoms. (4-b) R ^{5' s} are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. (8-2b) pieces of R ⁶ are each independently a hydrocarbon group having 1 to 8 carbon atoms, or —OR ⁷ (R ⁷ is a hydrocarbon group having 1 to 8 carbon atoms). B is an integer of 0 to 3.), a titanium chelate catalyst represented by the general formula (6):

(R ⁵ and R ⁶ are the same as described above. R ⁸ is a divalent hydrocarbon group having 1 to 20 carbon atoms.) A titanium chelate catalyst represented by the general formula (7):

(Wherein R ⁵ and R ⁶ are the same as described above),
A non-organotin-based adhesive composition for interior use according to (V), which is at least one selected from the group consisting of:
(VII). Furthermore, it is a non-organotin adhesive composition for interior use containing a plasticizer, wherein 10 to 100% by weight of the plasticizer component is a non-phthalate ester plasticizer (C) (I) to (VI ) Non-organotin-based adhesive composition for interior use according to any one of
(VIII). The non-phthalate ester plasticizer (C) is at least one selected from the group consisting of cyclohexanedicarboxylic acid diester, alkylsulfonic acid phenylester, and an oligomer made of an aromatic vinyl compound, according to (VII) Non-organotin adhesive composition for interior use,
(IX). Furthermore, the non-organotin-based adhesive composition for interior use according to any one of (I) to (VIII), comprising an epoxy group-containing silane coupling agent (D).
(X). Any one of (I) to (IX), wherein the 50% tensile stress is 0.3 MPa to 5 MPa when the cured product is measured with a 3 mm-thick dumbbell-shaped No. 3 test piece according to JIS K 6251 Non-organotin adhesive composition for interior according to item 1,
(XI). In accordance with JIS K 6253, non-organic tin for interior use according to any one of (I) to (X), wherein the hardness when the cured product is measured with a type A durometer is A10 to A90 Adhesive composition,
(XII). A cured product obtained by curing the interior non-organic tin adhesive composition according to any one of (I) to (XI),
About.

  The adhesive composition for interior use according to the present invention does not contain a demethanol-type organic polymer and an organic tin-based catalyst, and thus has high safety. Further, it has excellent curability, storage stability, adhesiveness, tensile stress, and hardness. Is also excellent.

  The present invention will be described in detail below.

  The adhesive composition of the present invention has an organic polymer (A) having a reactive silicon group having a specific structure as an essential component, and has a characteristic that a siloxane bond is formed by a reaction accelerated by a curing catalyst and is crosslinked. Here, the reactive silicon group is an organic group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and the organic polymer (A) has an average of one or more reactive silicon groups per molecule. Have. However, the reactive silicon group of the organic polymer (A) does not have a dimethoxymethylsilyl group or a trimethoxysilyl group that releases methanol with a hydrolysis reaction.

As the reactive silicon group of the organic polymer (A), the general formula (1):
-SiR ¹ _3-a X _a (1)
((3-a) pieces of R ¹ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and —OSi (R ² ). ₃ (R ² each independently represents a hydrocarbon group having 1 to 20 carbon atoms) is at least one selected from the group consisting of a triorganosiloxy group, and a number of X is each Independently, it is at least one selected from the group consisting of an ethoxy group, an isopropoxy group, an isopropenoxy group, and an acetoxy group, a is an integer of 1 to 3).

  The hydrolyzable group represented by X in the general formula (1) is any one of an ethoxy group, an isopropoxy group, an isopropenoxy group, and an acetoxy group. Among these, an ethoxy group is preferable because hydrolyzability is moderately mild and easy to handle. The hydrolyzable group can be bonded to one silicon atom in the range of 1 to 3, and when two or more hydrolyzable groups are bonded to the silicon atom in the reactive silicon group, they are It may be the same or different.

In addition, R ¹ in the general formula (1) is not particularly limited, and examples thereof include alkyl groups such as a methyl group and an ethyl group, cycloalkyl groups such as a cyclohexyl group, aryl groups such as a phenyl group, and benzyl groups. And the like, and among these, a methyl group is preferred.

Examples of the reactive silicon group represented by the general formula (1) include a triethoxysilyl group, a triisopropoxysilyl group, a triisopropenoxysilyl group, a triacetoxysilyl group, a diethoxymethylsilyl group, and a diisopropoxy group. Examples thereof include a methylsilyl group, a diisopropenoxymethylsilyl group, a diacetoxymethylsilyl group, and an ethoxydimethylsilyl group. Among these, since the alcohol produced | generated with a hydrolysis reaction is ethanol with high safety | security, a triethoxysilyl group, a diethoxymethylsilyl group, and an ethoxydimethylsilyl group are preferable. In addition, a triisopropenoxysilyl group, a triacetoxysilyl group, a diisopropenoxymethylsilyl group, and a diacetoxymethylsilyl group are preferred because of their rapid hydrolysis reaction and good curability. Furthermore, since an adhesive composition having good curability and storage stability is obtained, the reactive silicon group represented by the general formula (1) is a reactive silicon group represented by the general formula (2). It is preferable that a triethoxysilyl group, a triisopropenoxysilyl group, and a triacetoxysilyl group are more preferable, and a triethoxysilyl group is particularly preferable.
-SiX ₃ (2)
(X is the same as above.)
The method for introducing the reactive silicon group is not particularly limited, and examples thereof include known methods, and examples thereof include the following methods (a) to (c).

  (I). A polymer having a functional group such as a hydroxyl group in the molecule is reacted with an organic compound having an active group and an unsaturated group that are reactive with the functional group to obtain a polymer having an unsaturated group. Alternatively, a polymer having an unsaturated group is obtained by copolymerization with an epoxy compound having an unsaturated group. Next, a method of hydrosilylating the obtained reaction product by allowing hydrosilane having a reactive silicon group to act.

  (B). A method of reacting a compound having a mercapto group and a reactive silicon group with an organic polymer having an unsaturated group obtained in the same manner as in the method (a).

  (C). A method of reacting an organic polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in the molecule with a compound having a reactive functional group and a reactive silicon group.

  Among these methods, the method (a) or the method (c) in which a polymer having a hydroxyl group at the terminal is reacted with a compound having an isocyanate group and a reactive silicon group has a relatively short reaction time. Is preferable because a high conversion can be obtained. An adhesive composition mainly composed of an organic polymer having a reactive silicon group obtained by the method (a) is an adhesive composed mainly of an organic polymer obtained by the method (c). There is a tendency for the viscosity to be lower than that of the composition. As a result, an adhesive composition with good workability can be obtained. Further, the organic polymer obtained by the method (b) can be obtained by the method (b). Since the odor based on mercaptosilane is stronger than the obtained organic polymer, the method (A) is more preferable.

  The hydrosilane compound used in the method (a) is not particularly limited. For example, triethoxysilane, triisopropoxysilane, triisopropenoxysilane, triacetoxysilane, diethoxymethylsilane, diisopropoxymethylsilane , Diisopropenoxymethylsilane, diacetoxymethylsilane, diethoxyphenylsilane, diisopropoxyphenylsilane, 1- [2- (triethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane Etc. Among these, triethoxysilane and diethoxymethylsilane are preferable because the resulting adhesive composition containing the organic polymer as a main component has mild hydrolysis and is easy to handle. Triethoxysilane is preferred because it is easily available and the adhesive composition has excellent curability and storage stability.

  The synthesis method of (b) is not particularly limited, and for example, a compound having a mercapto group and a reactive silicon group is converted into an organic polymer by a radical addition reaction in the presence of a radical initiator and / or a radical source. Examples thereof include a method for introducing into an unsaturated binding site. The compound having a mercapto group and a reactive silicon group is not particularly limited. For example, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilaneethoxysilane, γ-mercaptopropyltriisopropenoxysilane, γ -Mercaptopropyltriacetoxysilane, γ-mercaptopropyldiethoxymethylsilane, γ-mercaptopropyldiisopropenoxymethylsilane, mercaptomethyltriethoxysilane, mercaptomethyltriisopropenoxysilane and the like.

  The method of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group in the synthesis method of (c) is not particularly limited, and is disclosed in, for example, JP-A-3-47825. And the like. The compound having an isocyanate group and a reactive silicon group is not particularly limited, and examples thereof include γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropyltriisopropoxysilane, γ-isocyanatepropyltriisopropenoxysilane, and γ-isocyanate. Propyltriacetoxysilane, γ-isocyanatopropyldiethoxymethylsilane, γ-isocyanatopropyldiisopropenoxymethylsilane, isocyanatemethyltriethoxysilane, isocyanatemethyltriisopropenoxysilane, isocyanatemethyldiethoxymethylsilane, isocyanatemethyldipropeno Examples include xylmethylsilane.

  A silane compound in which three hydrolyzable groups are bonded to one silicon atom such as triethoxysilane may cause a disproportionation reaction. When the disproportionation reaction proceeds, dangerous compounds such as diethoxysilane are produced.

  However, such disproportionation reaction does not proceed with γ-mercaptopropyltriethoxysilane or γ-isocyanatopropyltriethoxysilane. For this reason, when a group in which three hydrolyzable groups are bonded to one silicon atom such as a triethoxysilyl group is used as the silicon group, the synthesis method (b) or (c) may be used. preferable.

On the other hand, general formula (8):
H- (SiR ⁹ ₂ O) _n SiR ⁹ ₂ -R ¹⁰ -SiX ₃ (8)
(Three X's are the same as in the general formula (1). (2n + 2) R ^{9 s} are each independently a hydrocarbon group. R ¹⁰ is a divalent organic group. Is an integer of 19.), the disproportionation reaction does not proceed. For this reason, when a group in which three hydrolyzable groups are bonded to one silicon atom is introduced by the synthesis method (a), the silane compound represented by the general formula (8) should be used. Is preferred.

R ⁹ in the general formula (8) is not particularly limited as long as it is a hydrocarbon group, and among these, a hydrocarbon group having 1 to 20 carbon atoms is preferable from the viewpoint of availability and cost. A hydrocarbon group having 1 to 8 atoms is more preferable, and a hydrocarbon group having 1 to 4 carbon atoms is particularly preferable.

R ¹⁰ described in the general formula (8) is not particularly limited as long as it is a divalent organic group, and among these, a divalent hydrocarbon having 1 to 12 carbon atoms from the viewpoint of availability and cost. Group is preferable, a divalent hydrocarbon group having 2 to 8 carbon atoms is more preferable, and a divalent hydrocarbon group having 2 carbon atoms is particularly preferable.

  N described in the general formula (8) is an integer of 0 to 19, and among these, 1 is preferable from the viewpoint of availability and cost.

  Examples of the silane compound represented by the general formula (8) include 1- [2- (triethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane, 1- [2- (triethoxysilyl) Propyl] -1,1,3,3-tetramethyldisiloxane, 1- [2- (triethoxysilyl) hexyl] -1,1,3,3-tetramethyldisiloxane, and the like.

  As the organic polymer (A) having a reactive silicon group, any polymer having a linear or branched structure in the molecule can be used, and the number average molecular weight is measured by GPC. Is preferably in the range of 500 to 100,000. If the number average molecular weight is less than 500, the resulting cured product tends to be inferior in elongation characteristics, and if it exceeds 100,000, the adhesive composition tends to have high viscosity and tends to be inferior in workability. Moreover, in the adhesive composition which has an organic polymer (A) as a main component, since the tensile stress is large and a hardened adhesive cured product is obtained, the number average molecular weight of the organic polymer (A) is 1 1,000 to 50,000, more preferably 2,000 to 35,000, even more preferably 3,000 to 20,000, and particularly preferably 4,000 to 16,000.

  The number of reactive silicon groups contained in one molecule of the organic polymer (A) is preferably 1 or more, and preferably 1.1 to 5 as an average value. When the number of reactive silicon groups contained in the molecule is less than 1 on average, the adhesive composition tends to be inferior in curability, and the resulting cured product tends not to exhibit good rubber elastic behavior. There is.

  The reactive silicon group may be at the end of the main chain, at the end of the side chain, or at both. In particular, when the reactive silicon group is only at the end of the main chain, the effective network length of the organic polymer component contained in the resulting cured product is increased, so that the rubber exhibits high strength, high elongation, and low elastic modulus. It becomes easier to obtain a cured product.

  The main chain skeleton of the organic polymer (A) is not particularly limited. For example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxy Polyoxyalkylene polymers such as propylene-polyoxybutylene copolymers; ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or butadiene and acrylonitrile, and Carbonization of copolymers with styrene, etc., copolymers of polybutadiene, isoprene or copolymers of butadiene with acrylonitrile, styrene, etc., and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers Base polymer; polyester polymer obtained by condensation of dibasic acid such as adipic acid and glycol, or ring-opening polymerization of lactones; radical compounds such as ethyl (meth) acrylate and butyl (meth) acrylate (Meth) acrylic acid ester polymer obtained by polymerization; (meth) acrylic acid ester compound, vinyl polymer obtained by radical polymerization of vinyl acetate, acrylonitrile, styrene, etc .; Graft polymer obtained by polymerizing vinyl compound; Polysulfide polymer; Polyamide 6 by ring-opening polymerization of ε-caprolactam, Polyamide 6,6 by condensation polymerization of hexamethylenediamine and adipic acid, Hexamethylenediamine and sebacic acid Of Polyamide 6 · 10 and ε-aminoundecanoic acid by condensation polymerization of Polyamide 11 by ring-opening polymerization of ε-aminolaurolactam, polyamide-based polymer such as copolyamide composed of a plurality of the polyamides; polycarbonate-based polymers such as polycarbonate by condensation polymerization from bisphenol A and carbonyl chloride; Organic polymers such as diallyl phthalate polymers;

  Among these, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene and hydrogenated polybutadiene, organic polymers having polyoxyalkylene polymers and (meth) acrylic acid ester polymers in the main chain skeleton. Is preferable because the glass transition temperature is relatively low and the resulting cured product is excellent in cold resistance.

  The glass transition temperature of the organic polymer (A) is not particularly limited, is preferably 20 ° C. or less, more preferably 0 ° C. or less, and particularly preferably −20 ° C. or less. If the glass transition temperature exceeds 20 ° C., the viscosity of the adhesive composition in winter or cold regions tends to be high and workability tends to be poor, and the flexibility of the resulting cured product is reduced, resulting in a decrease in elongation. Tend to.

  The glass transition temperature can be determined by DSC measurement according to the measurement method defined in JIS K7121.

  In addition, an adhesive composition mainly composed of an organic polymer having a saturated hydrocarbon polymer, a polyoxyalkylene polymer, and a (meth) acrylic acid ester polymer as a main chain skeleton has a low molecular weight component. There are few transfer (contamination) etc. to adhesives, and it is more preferable.

  Furthermore, the organic polymer having a polyoxyalkylene polymer and a (meth) acrylic acid ester polymer in the main chain skeleton has high moisture permeability, and when used as a main component of a one-pack type adhesive, it is deeply cured. The cured product thus obtained is particularly preferable because of its excellent adhesiveness, and an organic polymer having a polyoxyalkylene polymer in the main chain skeleton is most preferable.

The polyoxyalkylene polymer used as the main chain skeleton of the organic polymer (A) has the general formula (9):
-R ¹¹ -O- (9)
(R ¹¹ is a linear or branched alkylene group having 1 to 14 carbon atoms).

R ¹¹ described in the general formula (9) is not particularly limited as long as it is a linear or branched alkylene group having 1 to 14 carbon atoms, and among these, a straight chain having 2 to 4 carbon atoms. Or a branched alkylene group is preferable.

The repeating unit represented by the general formula (9) is not particularly limited. For example, —CH ₂ O—, —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O—, —CH ₂ CH ( _{C 2 H 5) O -,} - CH 2 C (CH 3) 2 O -, - CH 2 CH 2 CH 2 CH 2 O-
Etc.

  The polyoxyalkylene polymer may be composed of only one type of repeating unit or may be composed of a plurality of types of repeating units. When used for adhesives, the organic polymer mainly composed of a propylene oxide polymer as the main chain skeleton is preferable because it is amorphous and has a relatively low viscosity.

  The production method of the polyoxyalkylene polymer is not particularly limited and includes known methods. For example, a method using an alkali catalyst such as KOH, an organoaluminum compound disclosed in JP-A-61-215623, Method using transition metal compound-porphyrin complex such as a complex obtained by reacting with porphyrin as a catalyst, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US US Pat. No. 3,278,595, US Pat. No. 3,427,256, US Pat. No. 3,427,334, US Pat. No. 3,427,335, etc., a method using a double metal cyanide complex as a catalyst, and a polyphosphazene salt disclosed in JP-A-10-273512 , Using as a catalyst, JP-A-11-0 Method or the like using a phosphazene compound disclosed in JP 0722 as catalyst.

  The production method of the polyoxyalkylene polymer having a reactive silicon group is not particularly limited, and examples thereof include known methods. For example, JP-B Nos. 45-36319, 46-12154, and JP-A-50-156599. No. 54-6096, No. 55-13767, No. 55-13468, No. 57-164123, No. 3-2450, US Pat. No. 3,362,557, US Pat. No. 4345053, US Pat. No. 4,366,307, US Pat. No. 4960844, etc., JP-A 61-197631, JP-A 61-215622, JP-A 61-215623, JP-A 61-218632, JP-A-3-72527, JP-A-3-47825, High molecular weight (number average molecular weight 6,000 or more) and molecular weight distribution disclosed in JP-A-8-231707 Narrow (Mw / Mn 1.6 or less) a method in which polymer is obtained and the like.

  When the polyoxyalkylene polymer having a reactive silicon group is blended in the adhesive composition, only one type may be blended or a plurality of types may be blended.

  The saturated hydrocarbon polymer used as the main chain skeleton of the organic polymer (A) refers to a polymer having substantially no carbon-carbon unsaturated bond other than an aromatic ring in the molecule, It has characteristics of excellent weather resistance, durability, and moisture barrier properties.

  The saturated hydrocarbon polymer is not particularly limited, and (i) a polymer composed of an olefin compound having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene and isobutylene as a repeating unit, (ii) repeating Examples thereof include a polymer comprising a diene compound such as butadiene and isoprene as a unit, and (iii) a polymer obtained by a method of copolymerizing the diene compound and the olefin compound, followed by hydrogenation. Among these, isobutylene-based polymers and hydrogenated polybutadiene-based polymers are preferable because it is easy to introduce functional groups at the ends, to easily control the molecular weight, and to adjust the number of terminal functional groups. More preferred.

  In the isobutylene polymer, all of the repeating units may be formed from isobutylene, or may be a copolymer with another compound. When an isobutylene-based copolymer is used as the main chain skeleton, a polymer having 50% by weight or more of repeating units derived from isobutylene per molecule is preferable because the rubber properties of the resulting cured product are excellent. % Or more is more preferable, and a polymer having 90 to 99% by weight is particularly preferable.

  The production method of the saturated hydrocarbon polymer is not particularly limited, and various conventionally known polymerization methods can be mentioned. Among these, a living polymerization method which has been developed in recent years is preferable. For example, as a method for producing an isobutylene polymer using a living polymerization method, an inifer polymerization (JP Kennedy et al., Found by Kennedy et al. J. Polymer Sci., Polymer Chem. Ed. 1997, 15, 2843).

  In this polymerization method, it is known that various functional groups can be introduced into the molecular terminals, and the resulting isobutylene polymer has a molecular weight distribution of 1.5 or less and a molecular weight of about 500 to 100,000.

  The method for producing the saturated hydrocarbon polymer having a reactive silicon group is not particularly limited, and examples thereof include known methods. For example, Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, and Japanese Patent Laid-Open No. Sho 63-63. Examples include methods disclosed in Japanese Patent No. 254149, Japanese Patent Application Laid-Open No. 64-22904, Japanese Patent Application Laid-Open No. 1-197509, Japanese Patent No. 2539445, Japanese Patent No. 2873395, Japanese Patent Application Laid-Open No. 7-53882, and the like.

  When the saturated hydrocarbon polymer having a reactive silicon group is blended in the adhesive composition, only one type may be blended or a plurality of types may be blended.

  The (meth) acrylic acid ester polymer used as the main chain skeleton of the organic polymer (A) is a polymer comprising a (meth) acrylic acid ester compound as a repeating unit. In addition, the said description method ((meth) acrylic acid ester) represents acrylic acid ester and / or methacrylic acid ester, and also represents the same meaning also in subsequent description methods.

  The (meth) acrylic acid ester compound used as the repeating unit is not particularly limited. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid n -Propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, (meth) acrylate n -Hexyl, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate , Dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, ( T) benzyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic Stearyl acid, glycidyl (meth) acrylate, γ- (methacryloyloxy) propyltrimethoxysilane, γ- (methacryloyloxy) propyldimethoxymethylsilane, ethylene oxide adduct of (meth) acrylic acid, trifluoro (meth) acrylic acid Methylmethyl, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, (meth) acrylic acid Perfluoroethyl, (meth) acrylic Trifluoromethyl oxalate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, ( Examples include (meth) acrylic acid compounds such as 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate.

  The (meth) acrylic acid ester polymer includes a copolymer of a (meth) acrylic acid ester compound and a vinyl compound copolymerizable therewith.

  The vinyl compound is not particularly limited, and examples thereof include styrene compounds such as styrene, vinyl toluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; silicon groups such as vinyltrimethoxysilane and vinyltriethoxysilane. A vinyl compound having: maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide , Maleimide compounds such as butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; acrylonitrile, methacrylate Vinyl compounds having a nitrile group such as nitrile; Vinyl compounds having an amide group such as acrylamide and methacrylamide; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; ethylene And alkenes such as propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and the like. A plurality of these can be used as a copolymerization component.

  Among the (meth) acrylic acid ester-based polymers obtained from the above-mentioned compounds, there is obtained a cured product obtained from an organic polymer having a copolymer consisting of a styrene compound and a (meth) acrylic acid compound as a main chain skeleton. The organic polymer having a main chain skeleton having a copolymer composed of an acrylate compound and a methacrylic acid ester compound is more preferable, and the organic polymer having a polymer comprising an acrylate compound in the main chain skeleton is more preferable. Coalescence is particularly preferred.

  Since the adhesive composition has a low viscosity and the obtained cured product is excellent in weather resistance and heat resistance, it is more preferable that the main chain skeleton of the organic polymer is composed of a butyl acrylate compound.

  Moreover, in the case of the adhesive agent used for an automotive use etc., as a hardened | cured material obtained, it is requested | required that it is excellent in oil resistance. As the cured product having excellent oil resistance, it is more preferable that the main chain skeleton of the organic polymer is a copolymer mainly composed of ethyl acrylate.

  The adhesive composition containing an organic polymer having a main chain skeleton of a copolymer mainly composed of ethyl acrylate tends to be slightly inferior in low-temperature characteristics (cold resistance) although the resulting cured product has excellent oil resistance. In order to improve the low temperature characteristics, a part of ethyl acrylate is replaced with butyl acrylate. However, as the ratio of butyl acrylate increases, its good oil resistance tends to be impaired. Therefore, when used in applications where oil resistance is required, the ratio is preferably 40% or less, Furthermore, it is more preferable to make it 30% or less.

  It is also preferable to use it for copolymer components such as 2-methoxyethyl acrylate and 2-ethoxyethyl acrylate in which oxygen is introduced into the side chain alkyl group in order to improve low-temperature characteristics and the like without impairing oil resistance. .

  However, since the resulting cured product tends to be inferior in heat resistance due to the introduction of an alkoxy group having an ether bond in the side chain, the ratio should be 40% or less when used in applications requiring heat resistance. Is preferred.

  As described above, an organic polymer having a main chain skeleton of a copolymer mainly composed of ethyl acrylate is an oil-resistant and heat-resistant material required for the resulting cured product according to various uses and required purposes. It is possible to obtain a suitable polymer by changing the type and ratio of the copolymer component in consideration of physical properties such as properties and low-temperature characteristics. For example, although not particularly limited, examples of excellent physical properties such as oil resistance, heat resistance, and low temperature characteristics include ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (40 to 50/20 by weight). To 30/30 to 20).

  In the present invention, these preferred compounds can be copolymerized with other compounds, and further block copolymerized. In this case, these preferred compounds may be contained in a weight ratio of 40% or more. preferable.

  It does not specifically limit as a manufacturing method of a (meth) acrylic-ester type polymer, A well-known method is mention | raise | lifted. Among these, the living radical polymerization method is preferably used because it is easy to introduce a crosslinkable functional group at the molecular chain terminal at a high ratio, and a polymer having a narrow molecular weight distribution and a low viscosity can be obtained.

  A polymer obtained by a normal free radical polymerization method using an azo compound, a peroxide or the like as a polymerization initiator generally has a large molecular weight distribution value of 2 or more and tends to have a high viscosity.

  Among the methods for producing a (meth) acrylic acid ester polymer using the “living radical polymerization method”, an “atom” using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst In addition to the characteristics of “Living Radical Polymerization”, which has a narrow molecular weight distribution and a low-viscosity polymer is obtained, the “transfer radical polymerization” has a large degree of freedom in selecting initiators and catalysts, and is suitable for functional group conversion reactions. It is more preferable as a method for producing a (meth) acrylic acid ester-based polymer having a specific functional group because it has a relatively advantageous halogen or the like at the terminal. Examples of the atom transfer radical polymerization method include Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614.

  The method for producing the (meth) acrylic acid ester-based polymer having a reactive silicon group is not particularly limited. For example, JP-B-3-14068, JP-B-4-55444, JP-A-6-221922 and the like The free radical polymerization method using the disclosed chain transfer agent, the atom transfer radical polymerization method disclosed in JP-A-9-272714 and the like can be mentioned.

  A (meth) acrylic ester copolymer comprising a plurality of the (meth) acrylic ester compounds can also be used as the main chain skeleton of the organic polymer (A).

As a specific example of the methacrylic ester copolymer comprising a plurality of (meth) acrylic ester compounds, the main chain skeleton is substantially represented by the general formula (10):
—CH ₂ —C (R ¹² ) (COOR ¹³ ) — (10)
(R ¹² is a hydrogen atom or a methyl group, R ¹³ is an alkyl group having 1 to 8 carbon atoms), and a repeating unit having an alkyl group having 1 to 8 carbon atoms,
General formula (11):
—CH ₂ —C (R ¹² ) (COOR ¹⁴ ) — (11)
(R ¹² is the same as in the general formula (10). R ¹⁴ is an alkyl group having 9 or more carbon atoms.) Coalesce.

R ¹³ in the general formula (10) is not particularly limited as long as it is an alkyl group having 1 to 8 carbon atoms. For example, methyl group, ethyl group, propyl group, n-butyl group, t-butyl group And 2-ethylhexyl group. Among these, an alkyl group having 1 to 4 carbon atoms is preferable, and an alkyl group having 1 or 2 carbon atoms is more preferable. Incidentally, R ¹³ contained in the copolymer is not necessarily limited to one kind of alkyl group.

R ¹⁴ described in the general formula (11) is not particularly limited as long as it is an alkyl group having 9 or more carbon atoms, and examples thereof include lauryl group, tridecyl group, cetyl group, stearyl group, and behenyl group. Among these, an alkyl group having 10 to 30 carbon atoms is preferable, and a long-chain alkyl group having 10 to 20 carbon atoms is more preferable. Incidentally, R ¹⁴ contained in the copolymer is not necessarily limited to one type of alkyl group.

  The (meth) acrylic ester copolymer is substantially composed of repeating units described in the general formula (10) and the general formula (11). Here, “substantially” means that the total proportion of the repeating units described in the general formulas (10) and (11) in the copolymer exceeds 50% by weight, and occupies the copolymer. The total proportion of the repeating units described in the general formulas (10) and (11) is preferably 70% by weight or more.

  Further, the ratio of the repeating units of the general formulas (10) and (11) present in the copolymer is preferably 95: 5 to 40:60 in weight ratio (general formula (10): general formula (11)). 90:10 to 60:40 is more preferable.

  The (meth) acrylic acid ester copolymer is a copolymer of a (meth) acrylic acid ester compound used as a repeating unit described in the general formulas (10) and (11) and a vinyl compound copolymerizable therewith. Includes coalescence.

  Examples of the vinyl compound include acrylic acid such as acrylic acid and methacrylic acid; amide groups such as acrylamide, methacrylamide, N-methylol acrylamide, and N-methylol methacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, and diethylaminoethyl acrylate. And compounds having an amino group such as diethylaminoethyl methacrylate and aminoethyl vinyl ether; and other compounds such as acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, and ethylene.

  In the main chain skeleton of the organic polymer (A), a repeating unit having, for example, a urethane bond other than those described above may be present as long as the effect of the present invention is not greatly impaired.

  The repeating unit having a urethane bond is not particularly limited, and examples thereof include a repeating unit having a group (hereinafter also referred to as an amide segment) generated by a reaction between an isocyanate group and an active hydrogen group.

The amide segment is represented by the general formula (12):
—NR ¹⁵ —C (═O) — (12)
(R ¹⁵ represents a hydrogen atom or an organic group).

  The amide segment is not particularly limited, and for example, a urethane group formed by a reaction between an isocyanate group and a hydroxyl group; a urea group formed by a reaction between an isocyanate group and an amino group; a group formed by a reaction between an isocyanate group and a mercapto group And thiourethane group.

  In the present invention, an organic group generated by a reaction of an active hydrogen in a urethane group, a urea group, and a thiourethane group with an isocyanate group is also defined as an amide segment.

A method for producing an organic polymer having a reactive silicon group having an amide segment in the main chain skeleton is not particularly limited, and examples thereof include Japanese Patent Publication No. 46-12154 (US Pat. No. 3,632,557) and Japanese Patent Publication No. 58-109529. (U.S. Pat. No. 4,374,237), JP-A-62-143030 (U.S. Pat. No. 4,645,816), JP-A-8-53528 (EP0676403), JP-A-10-204144 (EP0831108), JP-T-2003-508561 (US Pat. No. 6,1979,912) No. 6-2111879 (U.S. Pat. No. 5,364,955), JP-A No. 10-53637 (U.S. Pat. No. 5,757,751), JP-A Nos. 11-100197, 2000-169544, 2000-169545, JP 2002-212415 A, Patent No. 3313 No. 60, U.S. Pat. No. 4,067,844, U.S. Pat. No. 3,711,445, JP-A No. 2001-323040, etc., and an organic polymer having an organic group having an active hydrogen at the terminal are reacted with an excess amount of a polyisocyanate compound. Thus, after obtaining a polymer having an isocyanate group at the terminal of the polyurethane main chain, or at the same time, all or part of the isocyanate group in the polymer and the general formula (13):
W-R ¹⁶ -SiR ¹ _3-a X _a (13)
(R ¹ , X and a are the same as those in the general formula (1). R ¹⁶ is a divalent organic group, more preferably a divalent hydrocarbon group having 1 to 20 carbon atoms. A method of reacting W in a silicon compound represented by a hydroxyl group, a carboxyl group, a mercapto group, and an amino group (primary or secondary group having at least one active hydrogen selected from the group consisting of primary and secondary). can give.

JP-A-11-279249 (US Pat. No. 5,990,257), JP-A 2000-119365 (US Pat. No. 6046270), JP-A 58-29818 (US Pat. No. 4345053), JP-A-3-47825 (US) Patent No. 5068304), JP-A-11-60724, JP-A-2002-155145, JP-A-2002-249538, WO03 / 018658, WO03 / 059981, and the like. Group having hydrogen and general formula (14):
O = C = N-R ¹⁶ -SiR ¹ _3-a X _a (14)
(R ¹ , R ¹⁶ , X, and a are the same as those in the general formula (1) and the general formula (13)). A method of reacting an isocyanate group of an isocyanate compound having a reactive silicon group represented by the general formula (1). .

  The organic polymer having a group having an active hydrogen at the terminal is not particularly limited. For example, an oxyalkylene polymer having a hydroxyl group at the terminal (polyether polyol), a polyacryl polyol, a polyester polyol, and a saturated hydroxyl group at the terminal. Examples thereof include hydrocarbon polymers (polyolefin polyol), polythiol compounds, polyamine compounds and the like.

  Among these, polyether polyols, polyacrylic polyols, and organic polymers having a polyolefin polyol component in the main chain skeleton are preferable because the glass transition temperature is relatively low and the resulting cured product is excellent in cold resistance.

  An organic polymer containing a polyether polyol component is particularly preferred because it has a low viscosity and good workability, and the resulting cured product has good deep curability and adhesiveness. Moreover, the adhesive composition using the polyacryl polyol and the organic polymer having a saturated hydrocarbon polymer component is more preferable because the obtained cured product has good weather resistance and heat resistance.

  As the polyether polyol, those having an average of at least 0.7 hydroxyl groups per molecule are preferred.

  The production method is not particularly limited and includes known methods. For example, at least two polymerization methods using an alkali metal catalyst, at least two per molecule as an initiator in the presence of a double metal cyanide complex or cesium. Examples thereof include a polymerization method of alkylene oxide using a polyhydroxy compound having a hydroxyl group.

  Among the above polymerization methods, a polymerization method using a double metal cyanide complex has a low degree of unsaturation, a narrow molecular weight distribution (Mw / Mn), and a low viscosity polymer can be obtained. It is preferable due to excellent acid resistance and weather resistance.

  The polyacryl polyol refers to a polyol having a (meth) acrylic acid alkyl ester (co) polymer as a skeleton and having a hydroxyl group in the molecule.

  The production method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the resulting polymer has a narrow molecular weight distribution and can be reduced in viscosity. Further, a polymerization method based on a so-called SGO process in which an alkyl acrylate ester compound disclosed in JP-A-2001-207157 is continuously bulk-polymerized at high temperature and high pressure is preferable. Examples of the polyacryl polyol include Alfon UH-2000 manufactured by Toagosei Co., Ltd.

  The polyisocyanate compound is not particularly limited, and examples thereof include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate. It is done.

  The silicon compound represented by the general formula (13) is not particularly limited, and examples thereof include γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, and γ- (N-phenyl). ) Having amino groups such as aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, etc. Silane compounds; silane compounds having a hydroxy group such as γ-hydroxypropyltrimethoxysilane; silane compounds having a mercapto group such as γ-mercaptopropyltrimethoxysilane;

  Furthermore, as the silicon compound described in the general formula (14), JP-A-6-2111879 (US Pat. No. 5,364,955), JP-A-10-53637 (US Pat. No. 5,757,751), JP-A-10-204144 (EP0831108), Michael addition reaction products of various α, β-unsaturated carbonyl compounds and silane compounds having a primary amino group disclosed in JP-A Nos. 2000-169544 and 2000-169545, or various types of (meth) Examples include a Michael addition reaction product of a silane compound having an acryloyl group and a compound having a primary amino group.

  The isocyanate compound having a reactive silicon group described in the general formula (14) is not particularly limited. For example, γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, γ-methyldimethoxysilylpropyl isocyanate, γ -Methyldiethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate and the like.

  Furthermore, as the isocyanate compound having a reactive silicon group described in the general formula (14), an excessive amount of the silicon compound described in the general formula (13) disclosed in JP-A No. 2000-119365 (US Pat. No. 6,046,270) Examples include reaction products of polyisocyanate compounds.

  In the present invention, a titanium catalyst (B) is used. This titanium catalyst (B) functions as a curing catalyst for the organic polymer (A).

  Conventionally, organic tin catalysts such as dibutyltin dilaurate and dibutyltin diacetylacetonate have been used as curing catalysts for the organic polymer (A) having a reactive silicon group. These organic tin catalysts are toxic. Has been pointed out. Since the organotin catalyst has a toxic or environmental load depending on the amount of the catalyst added, the non-organotin adhesive composition of the present invention substantially contains an organotin catalyst in the composition. It is characterized by not. Here, “substantially does not contain” means that the content of the organotin catalyst with respect to 100 parts by weight of the organic polymer (A) is 0.5 parts by weight or less. The content of the organotin catalyst is preferably 0.1 parts by weight or less, more preferably 0.01 parts by weight or less, and particularly preferably not contained at all.

A compound such as TiO ₂ that does not function as a curing catalyst for the organic polymer (A) is not included in the component (B) of the present invention.

The titanium catalyst (B) is a compound having a titanium atom bonded to a hydroxyl group or an alkoxy group, and preferred specific examples of the titanium catalyst (B) include a compound represented by the general formula (3):
Ti (OR ³ ) ₄ (3)
(R ³ is an organic group, and four R ^{3 s} may be the same or different from each other.) And / or the general formula (4):
O = Ti (OR ³ ) ₂ (4)
(R ³ is the same as described above).

Among these, titanium alkoxide can be exemplified as a representative compound. In addition, as the titanium catalyst represented by the general formula (3) and the general formula (4), a part or all of the OR ³ groups described in the general formula (3) and the general formula (4) (15):
-OCOR ¹⁷ (15)
(R ¹⁷ is an organic group, and more preferably a hydrocarbon group having 1 to 20 carbon atoms).

Moreover, as a titanium catalyst other than the titanium catalyst represented by General Formula (3) and General Formula (4), General Formula (16):
TiX ² _4-c (OR ¹⁸ ) _c (16)
(X ² is a halogen atom, and (4-c) X ^{2 s} may be the same or different from each other. R ¹⁸ is an organic group, more preferably 1 to 20 carbon atoms. And c R ^{18 s} may be the same or different from each other, c is an integer of 1 to 3).

  Among these, titanium alkoxide is preferable from the viewpoints of stability to moisture and curability.

  Of the titanium catalysts represented by the general formula (3) and the general formula (4), a titanium chelate is preferable, and among these, the general formula (5):

(B R ^{4 's} are each independently a hydrocarbon group having 1 to 20 carbon atoms. (4-b) R ^{5' s} are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. (8-2b) pieces of R ⁶ are each independently a hydrocarbon group having 1 to 8 carbon atoms, or —OR ⁷ (R ⁷ is a hydrocarbon group having 1 to 8 carbon atoms). B is an integer of 0 to 3.), a titanium chelate catalyst represented by the general formula (6):

(R ⁵ and R ⁶ are the same as described above. R ⁸ is a divalent hydrocarbon group having 1 to 20 carbon atoms.) A titanium chelate catalyst represented by the general formula (7):

(R ⁵ and R ⁶ are the same as described above), and the titanium chelate catalyst is more preferable from the viewpoints of compatibility with the organic polymer (A), high catalytic activity, and storage stability.

  The titanium chelate catalyst represented by the general formula (5) is particularly preferable because of its high catalytic activity. The titanium chelate catalyst in which b is 2 described in the general formula (5) is particularly preferable because it has relatively low crystallinity (melting point), good workability, and high catalytic activity. Moreover, the titanium chelate catalyst represented by the general formula (7) is particularly preferable because an adhesive composition having a large tensile stress can be obtained.

  Of the compounds represented by general formula (3) and general formula (4), specific examples of titanium alkoxide include titanium tetramethoxide, titanium tetraethoxide, titanium tetraallyl oxide, titanium tetra n-propoxide, Titanium tetraisopropoxide, Titanium tetra n-butoxide, Titanium tetraisobutoxide, Titanium tetra sec-butoxide, Titanium tetra t-butoxide, Titanium tetra n-pentyl oxide, Titanium tetracyclopentyl oxide, Titanium tetrahexyl oxide, Titanium tetracyclohexyl oxide , Titanium tetrabenzyl oxide, titanium tetraoctyl oxide, titanium tetrakis (2-ethylhexyl oxide), titanium Tetradecyl oxide, titanium tetradodecyl oxide, titanium tetrastearyl oxide, titanium tetrabutoxide dimer, titanium tetrakis (8-hydroxyoctyl oxide), titanium diisopropoxide bis (2-ethyl-1,3-hexanediolato), titanium Bis (2-ethylhexyloxy) bis (2-ethyl-1,3-hexanediolato), titanium tetrakis (2-chloroethoxide), titanium tetrakis (2-bromoethoxide), titanium tetrakis (2-methoxyethoxide) ), Titanium tetrakis (2-ethoxyethoxide), titanium butoxide trimethoxide, titanium dibutoxide dimethoxide, titanium butoxide triethoxide, titanium dibutoxide Ethoxide, Titanium butoxide triisopropoxide, Titanium dibutoxide diisopropoxide, Titanium tetraphenoxide, Titanium tetrakis (o-chlorophenoxide), Titanium tetrakis (m-nitrophenoxide), Titanium tetrakis (p-methylphenoxide), Titanium tetrakis (Trimethylsilyloxide), dimethoxyoxotitanium, dietoxoxotitanium, di-n-propoxyoxotitanium, diisopropoxyoxotitanium, di-n-butoxyoxotitanium, diisobutoxyoxotitanium, dit-butoxyoxotitanium, dimetatitanate di ( 2-hydroxyethyl) and the like.

Specific examples of the titanium carboxylate in which part or all of the OR ³ groups described in the general formula (3) and the general formula (4) are groups represented by the general formula (15): Examples thereof include isopropoxide, titanium methacrylate triisopropoxide, titanium dimethacrylate diisopropoxide, titanium isopropoxide trimethacrylate, titanium hexanoate triisopropoxide, titanium stearate triisopropoxide and the like.

  Specific examples of the halogenated titanium alkoxide of the general formula (16) include titanium chloride triisopropoxide, titanium dichloride diisopropoxide, titanium isopropoxide trichloride, titanium bromide triisopropoxide, titanium fluoride triiso Examples thereof include propoxide, titanium chloride triethoxide, titanium chloride tributoxide and the like.

  Specific examples of titanium chelates of general formula (5), general formula (6), and general formula (7) include titanium dimethoxide bis (ethyl acetoacetate), titanium dimethoxide bis (acetylacetonate), and titanium diethoxy. Dobis (ethyl acetoacetate), titanium dietobisbis (acetylacetonate), titanium diisopropoxide bis (ethyl acetoacetate), titanium diisopropoxide bis (methyl acetoacetate), titanium diisopropoxide bis (t -Butylacetoacetate), titanium diisopropoxide bis (methyl-3-oxo-4,4-dimethylhexanoate), titanium diisopropoxide bis (ethyl-3-oxo-4,4,4-trifluorobutene) Tanoate), titanium Isopropoxide bis (acetylacetonate), titanium diisopropoxide bis (2,2,6,6-tetramethyl-3,5-heptanedionate), titanium di-n-butoxide bis (ethylacetoacetate), Titanium di-n-butoxide bis (acetylacetonate), Titanium diisobutoxide bis (ethyl acetoacetate), Titanium diisobutoxide bis (acetylacetonate), Titanium di-t-butoxide bis (ethyl acetoacetate), Titanium di -T-butoxide bis (acetylacetonate), titanium di-2-ethylhexoxide bis (ethyl acetoacetate), titanium di-2-ethylhexoxide bis (acetylacetonate), titanium bis (1-methoxy- 2-propo Sid) bis (ethyl acetoacetate), titanium bis (3-oxo-2-butoxide) bis (ethyl acetoacetate), titanium bis (3-diethylaminopropoxide) bis (ethyl acetoacetate), titanium triisopropoxide (ethyl) Acetoacetate), titanium triisopropoxide (diethyl malonate), titanium triisopropoxide (allyl acetoacetate), titanium triisopropoxide (methacryloxyethyl acetoacetate), 1,2-dioxyethane titanium bis (ethyl) Acetoacetate), 1,3-dioxypropane titanium bis (ethyl acetoacetate), 2,4-dioxypentane titanium bis (ethyl acetoacetate), 2,4-dimethyl-2,4-dioxy Pentane titanium bis (ethyl acetoacetate), titanium diisopropoxide bis (triethanolaminate), titanium tetrakis (ethyl acetoacetate), titanium tetrakis (acetylacetonate), titanium bis (trimethylsiloxy) bis (ethyl acetoacetate) , Titanium bis (trimethylsiloxy) bis (acetylacetonate), oxotitanium (1,2-benzenediolate), oxobis (2,4-pentanedionato) titanium, oxobis (ethylacetoacetate) titanium and the like.

  Among these, titanium diethoxide bis (ethyl acetoacetate), titanium diethoxide bis (acetylacetonate), titanium diisopropoxide bis (ethylacetoacetate), titanium diisopropoxide bis (acetylacetonate), titanium di Butoxide bis (ethyl acetoacetate), titanium dibutoxide bis (acetylacetonate), and oxobis (2,4-pentanedionato) titanium are preferable from the viewpoint of availability and catalytic activity, and titanium diethoxide bis (ethyl acetoacetate). ), Titanium diisopropoxide bis (ethyl acetoacetate), titanium dibutoxide bis (ethyl acetoacetate), oxobis (2,4-pentanedionato) titanium, more preferably titanium Isopropoxide bis (ethylacetoacetate) are particularly preferred. Titanium diisopropoxide bis (ethyl acetoacetate) is commercially available from Matsumoto Pharmaceutical Co., Ltd. under the trade name ORGATICS TC-750, and from DuPont Co., Ltd. under the trade name Tiza PITA, and is easily available.

  Specific examples of titanium catalysts other than those described above include titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzene sulfonate) isopropoxide, and dihydroxytitanium bislactate.

  Specific examples of the chelating reagent capable of forming a chelate ligand of the titanium chelate include β-diketones such as acetylacetone, 2,2,4,4-tetramethyl-3,5-heptanedione, and methyl acetoacetate. , Ethyl acetoacetate, t-butyl acetoacetate, allyl acetoacetate, acetoacetic acid (2-methacryloxyethyl), methyl 3-oxo-4,4-dimethylhexanoate, 3-oxo-4,4,4-trifluoro Β-ketoesters such as ethyl butanoate; β-diesters such as dimethyl malonate and diethyl malonate; are preferred from the viewpoint of curability. Among these, β-diketone and β-ketoester are more preferable from the viewpoint of curability and storage stability, and β-ketoester is particularly preferable. From the viewpoints of curability, storage stability and availability, acetylacetone, methyl acetoacetate and ethyl acetoacetate are more preferred, and ethyl acetoacetate is particularly preferred. When two or more chelate ligands are present, each chelate ligand may be the same or different.

  As a method of adding the titanium chelate, besides directly adding the titanium chelate exemplified above, a titanium compound capable of reacting with a chelating reagent such as titanium tetraisopropoxide or titanium dichloride diisopropoxide, ethyl acetoacetate, etc. The chelating reagent may be added to the composition of the present invention and chelated in the composition.

  A titanium catalyst (B) may mix | blend only 1 type when mix | blending with an adhesive composition, and may mix | blend multiple types in combination. As a compounding quantity of a titanium catalyst (B), 0.01-20 weight part is preferable with respect to 100 weight part of organic polymers (A), 0.1-15 weight part is more preferable, 0.5-10 Part by weight is more preferable, and 1 to 5 parts by weight is particularly preferable. When the compounding amount of the titanium catalyst (B) is 0.01 to 20 parts by weight, the adhesive composition has more excellent curability and has an appropriate curing time, and therefore has excellent workability. Become.

  The adhesive composition of the present invention uses the titanium catalyst (B) as a curing catalyst, but other curing catalysts can be added to the extent that the effects of the present invention are not impaired as required.

  The curing catalyst other than the titanium catalyst (B) is not particularly limited. For example, tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate Carboxylic acid metal salts such as hafnium carboxylate, vanadium carboxylate, manganese carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, cerium carboxylate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate , Dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate), dibutyltin bis (ethylmaleate), dibutyltin bis (butylmaleate), dibutyltin bis (octylmaleate), dibuty Tin bis (tridecyl maleate), dibutyl tin bis (benzyl maleate), dibutyl tin diacetate, dioctyl tin bis (ethyl maleate), dioctyl tin bis (octyl maleate), dibutyl tin dimethoxide, dibutyl tin bis (nonyl) Organic tin compounds such as phenoxide), dibutenyl tin oxide, dibutyltin oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetoacetonate); aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate) ), Aluminum compounds such as diisopropoxy aluminum ethyl acetoacetate; zirconium compounds such as zirconium tetrakis (acetylacetonate); various metal alcohols such as tetrabutoxy hafnium Sid like; organic acid phosphate esters; organic sulfonic acids such as trifluoromethanesulfonic acid; hydrochloric acid, phosphoric acid, inorganic acids such as boronic acid, and the like.

  When the curing catalyst other than the titanium catalyst (B) is used in combination, the catalytic activity is increased, and improvement in deep part curability, thin layer curability, adhesion, and the like is expected.

  However, from the viewpoint of toxicity, it is preferable that the amount of the organotin catalyst added is small. In the present non-organotin-based adhesive composition, the amount of the organic tin-based catalyst added is preferably 50% by weight or less, more preferably 30% by weight or less in the compound component acting as a curing catalyst. % By weight or less is more preferred, 1% by weight or less is particularly preferred, and most preferably it is not contained. Furthermore, in consideration of environmental burden, a non-tin adhesive composition that substantially does not contain a tin compound such as an organic tin compound or tin carboxylate is more preferable.

  A plasticizer is added to the adhesive composition of the present invention as necessary. By adding the plasticizer, the viscosity and slump property of the adhesive composition, and the mechanical properties such as tensile strength and elongation of the obtained cured product can be adjusted.

  Examples of commonly used plasticizers include phthalate plasticizers such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate. These phthalate ester plasticizers have been used widely as low-viscosity and inexpensive plasticizers, and may be added to the adhesive composition of the present invention. However, since the phthalic acid ester compound is suspected of being an environmental hormone and there is a concern about the influence on the human body, it is preferable that the addition amount to the adhesive composition of the present invention is small. Therefore, when adding a plasticizer to the adhesive composition of the present invention, it is preferable to add a non-phthalate ester plasticizer (C). That is, 10% by weight or more of the plasticizer component is preferably a non-phthalate ester plasticizer (C), more preferably 30% by weight or more is a non-phthalate ester plasticizer (C), More preferably, 50% by weight or more is a non-phthalate plasticizer (C), more preferably 80% by weight or more is a non-phthalate plasticizer (C), and 100% by weight is non-phthalate. The acid ester plasticizer (C) is most preferable.

  The non-phthalate ester plasticizer (C) mentioned here is a plasticizer having no phthalate ester structure in the molecule. The non-phthalate ester plasticizer (C) is an environmentally friendly compound unlike a so-called environmental hormone called phthalate ester compound, and has little adverse effect on the human body.

  As the non-phthalic ester plasticizer (C), from the viewpoint of availability and safety, any of oligomers composed of cyclohexanedicarboxylic acid diester, alkylsulfonic acid phenylester, and aromatic vinyl compound is more preferable. Among these, since the obtained adhesive composition is excellent in storage stability, an oligomer composed of a cyclohexanedicarboxylic acid diester and an aromatic vinyl compound is preferable, and a cyclohexanedicarboxylic acid diester is more preferable.

  Specific examples of the cyclohexane dicarboxylic acid diester include cyclohexane dicarboxylic acid dimethyl ester, cyclohexane dicarboxylic acid diethyl ester, cyclohexane dicarboxylic acid dibutyl ester, cyclohexane dicarboxylic acid diisobutyl ester, cyclohexane dicarboxylic acid dinormal hexyl ester, cyclohexane dicarboxylic acid bis (2-ethylhexyl). ) Ester, cyclohexanedicarboxylic acid dinormal octyl ester, cyclohexanedicarboxylic acid diisononyl ester, cyclohexanedicarboxylic acid dinonyl ester, cyclohexanedicarboxylic acid diisodecyl ester, cyclohexanedicarboxylic acid diisoundecyl ester, cyclohexanedicarboxylic acid bisbutylbenzyl ester, etc. , The present invention is not limited to these.

  Among these, cyclohexanedicarboxylic acid bis (2-ethylhexyl) ester, cyclohexanedicarboxylic acid diisononyl ester, cyclohexanedicarboxylic acid diisodecyl ester, from the viewpoint of compatibility with the organic polymer (A) and the plasticizing effect given to the adhesive composition, Cyclohexanedicarboxylic acid diisoundecyl ester is preferred, and cyclohexanedicarboxylic acid diisononyl ester is particularly preferred. Cyclohexanedicarboxylic acid diisononyl ester is commercially available from BASF Corp. under the trade name Hexamol DINCH and is readily available.

  Examples of the oligomer composed of an aromatic vinyl compound include dimers, trimers, and tetramers of aromatic vinyl compounds such as styrene, vinyl toluene, α-methylstyrene, and chlorostyrene. In this case, all the molecules constituting the oligomer may be the same molecule, homodimer, homotrimer, or homotetramer, or the molecules constituting the oligomer may be different, heterodimer, heterotrimer, heterotrimer. .

  Examples of the oligomer comprising an aromatic vinyl compound include the aromatic vinyl compound and a compound copolymerizable therewith, for example, acrylic acid such as acrylic acid and methacrylic acid; acrylamide, methacrylamide, N-methylolacrylamide, and N-methylol. Compounds having amide groups such as methacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, amino groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether; other acrylonitrile, alkyl vinyl ether, vinyl chloride, vinyl acetate, propionic acid It may be an oligomer made of a compound such as vinyl or ethylene.

  Oligomers composed of aromatic vinyl compounds are commercially available from Rutgers Chemical Co., Ltd. under the trade name Novales L100, and are easily available.

  Alkyl sulfonic acid phenyl ester is commercially available from LANXESS Co., Ltd. under the trade name Mezamol II, and is easily available.

  Other non-phthalate ester plasticizers (C) include non-aromatic dibasic acid esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate; butyl oleate, methyl acetylricinoleate, etc. Aliphatic esters; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Chlorinated paraffins; Hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; Process oils And epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

  As the non-phthalate ester plasticizer (C), a polymer plasticizer having a molecular weight of 500 or more can also be used. When a high-molecular plasticizer is used, the initial physical properties are maintained over a long period of time as compared with the case where a low-molecular plasticizer that is a plasticizer containing no polymer component in the molecule is used. Furthermore, the drying property (also referred to as paintability) when an alkyd paint is applied to the cured product can be improved. Specific examples of the polymer plasticizer include vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; Polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; Is a polyether polyol of 1000 or more such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like. Polyethers derivatives converted to like; polybutadiene, polybutene, polyisobutylene, butadiene - acrylonitrile, although polychloroprene, and the like, but is not limited thereto.

  When these polymer plasticizers are used in combination with the titanium catalyst (B), it is preferable because an adhesive composition in which the curability is hardly lowered after storage can be obtained. Of these, polyethers are preferable, and polypropylene glycol is more preferable. The polymer plasticizer is preferably compatible with the organic polymer (A). From this point, polyethers and vinyl polymers are preferable. From the viewpoints of compatibility, weather resistance, and heat resistance, vinyl polymers are preferred. Among vinyl polymers, acrylic polymers and / or methacrylic polymers are preferred, and acrylic polymers such as polyacrylic acid alkyl esters are more preferred. The polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered. Moreover, it is preferable to use a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of an alkyl acrylate monomer described in JP-A-2001-207157 at high temperature and high pressure.

  The number average molecular weight of the polymer plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, still more preferably 1,000 to 8,000, particularly preferably 1,000 to. 5,000. Most preferably, it is 1,000-3,000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and rain, the initial physical properties cannot be maintained over a long period of time, and the alkyd paintability cannot be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will worsen. The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and is preferably less than 1.80. 1.70 or less is more preferable, 1.60 or less is more preferable, 1.50 or less is more preferable, 1.40 or less is particularly preferable, and 1.30 or less is most preferable.

  The number average molecular weight is measured by a GPC method in the case of a vinyl polymer, and by a terminal group analysis method in the case of a polyether polymer. Moreover, it is measured by molecular weight distribution (Mw / Mn) GPC method (polystyrene conversion).

  The polymer plasticizer may not have a reactive silicon group, but may have a reactive silicon group. When it has a reactive silicon group, it acts as a reactive plasticizer and can prevent migration of the plasticizer from the cured product. In the case of having a reactive silicon group, the average number per molecule is preferably 1 or less, more preferably 0.8 or less. When using a plasticizer having a reactive silicon group, particularly an oxyalkylene polymer having a reactive silicon group, the number average molecular weight thereof must be lower than that of the organic polymer (A).

  When blending the plasticizer in the adhesive composition, only one kind may be blended, or a plurality of kinds may be blended. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. These plasticizers can also be blended at the time of polymer production. As a compounding quantity of a plasticizer, 5-300 weight part is preferable with respect to 100 weight part of organic polymers (A), 10-200 weight part is more preferable, 20-100 weight part is still more preferable, 40-80 Part by weight is particularly preferred. If the blending amount of the plasticizer is less than 5 parts by weight, sufficient plasticization may not be obtained and workability may be deteriorated. If the blending amount exceeds 300 parts by weight, the adhesion to the base material is degraded. There is a case.

  On the other hand, when the number average molecular weight of the organic polymer (A) used is small and the resulting adhesive composition has a low viscosity and excellent workability, it is better not to add a plasticizer to shift the plasticizer to the adherend. This is preferable because there is little (contamination) and the like, and the influence on the human body and the load on the environment are reduced. In this case, the number average molecular weight of the organic polymer (A) is preferably 50,000 or less, more preferably 35,000 or less, still more preferably 20,000 or less, and particularly preferably 16,000 or less. In addition, the smaller the number average molecular weight of the organic polymer (A) used in this way is, the more preferable it is because the resulting adhesive composition tends to have better curability.

  A silane coupling agent is added to the adhesive composition of the present invention as necessary. Here, the silane coupling agent is a compound having a hydrolyzable silicon group and other functional groups in the molecule, and by blending in the adhesive composition, the cured product obtained can be bonded to various adherends. It shows the effect of improving the property, and the effect of removing (dehydrating) water contained in the adhesive composition. The silane coupling agent is a compound that can function as a physical property modifier, an inorganic filler dispersibility improver, and the like in addition to the above-described effects.

Examples of the hydrolyzable silicon group present in the silane coupling agent include those in which X in the general formula (1): —SiR ¹ _a X _3-a is a hydrolyzable group. The hydrolyzable group is not particularly limited. For example, specifically, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group And alkenyloxy groups. Among these, a methoxy group, an ethoxy group, and the like are preferable because they have an appropriate hydrolysis rate. The number of hydrolyzable groups contained in one molecule of the silane coupling agent is preferably 2 or more, particularly 3 or more.

  Examples of functional groups other than hydrolyzable silicon groups present in silane coupling agents include substituted or unsubstituted amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, halogens, etc. it can. Among these, the silane coupling agent (D) having an epoxy group is preferable because the adhesiveness between the obtained cured product and the adherend is particularly improved. Moreover, the silane coupling agent (D) which has an epoxy group is preferable also from the viscosity increase of the adhesive composition with time etc. being suppressed and being able to preserve | save for a long time in a favorable state.

  The silane coupling agent (D) having an epoxy group is not particularly limited. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxy Silane, γ-glycidoxypropyltriisopropenoxysilane, γ-glycidoxypropyltriacetoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriisopropoxysilane, β- (3,4-epoxycyclohexyl) ethyltriisopropenoxysilane, β- (3,4-epoxycyclohexyl) ethyl Epoxysilanes such as lutriacetoxysilane are exemplified.

  Among the silane coupling agents (D) having an epoxy group, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ from the viewpoint of good compatibility, transparency, and availability. -Glycidoxypropyltriisopropenoxysilane, γ-glycidoxypropyltriacetoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is preferable, γ-glycidoxypropyltriethoxysilane, γ- Glycidoxypropyltriisopropenoxysilane is more preferable, and γ-glycidoxypropyltriethoxysilane is particularly preferable.

  Moreover, silane coupling agents other than the silane coupling agent (D) which has an epoxy group can also be added, for example, (gamma) -aminopropyltrimethoxysilane, (gamma) -aminopropyltriethoxysilane, (gamma) -aminopropyltriisosilane. Propoxysilane, γ-aminopropyltriisopropenoxysilane, γ-aminopropyltriacetoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxy Silane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2- Aminoethyl) aminopropyl Liisopropoxysilane, γ- (2-aminoethyl) aminopropyltriisopropenoxysilane, γ- (2-aminoethyl) aminopropyltriacetoxysilane, γ- (2- (2-aminoethyl) aminoethyl) amino Propyltriethoxysilane, γ- (6-aminohexyl) aminopropyltriethoxysilane, 3- (N-ethylamino) -2-methylpropyltriethoxysilane, 2-aminoethylaminomethyltriethoxysilane, N-cyclohexylamino Methyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenylaminomethyltriethoxy Sisilane, N-benzyl-γ-aminopropyltriethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N-cyclohexylaminomethyl Triethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, N-phenylaminomethyltriethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, (2-aminoethyl) Aminosilanes such as aminomethyltriethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine; N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1- Ketimines such as propanamine Silanes: γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, (isocyanatemethyl) trimethoxysilane, (isocyanatemethyl) dimethoxy Isocyanate silanes such as methylsilane, (isocyanatemethyl) triethoxysilane, (isocyanatemethyl) diethoxymethylsilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ -Mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, etc. Carboxysilanes such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltriisopropenoxysilane, vinyltriacetoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltriethoxysilane, methacryloyloxymethyltrimethoxy Vinyl type unsaturated group-containing silanes such as silane; Halogen-containing silanes such as γ-chloropropyltrimethoxysilane and γ-chloropropyltriethoxysilane; Tris (3-trimethoxy Isocyanurate silanes such as silylpropyl) isocyanurate; and the like. Moreover, the reaction product of the said aminosilanes and epoxysilanes, the reaction product of aminosilanes and isocyanate silanes, etc. can be used. Condensates obtained by partially condensing the silanes can also be used. Furthermore, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters and the like, which are derivatives of these, can also be used as silane coupling agents. .

  However, care must be taken because the catalytic activity of the titanium catalyst (B) may be reduced depending on the type of aminosilane to be added. In particular, aminosilanes having a primary amino group are preferably not used because they tend to reduce the catalytic activity of the titanium catalyst (B).

  When selecting the silane coupling agent, a hydrolyzable group having the same structure as the hydrolyzable group of the organic polymer (A) is used for the purpose of preventing the curability of the adhesive composition from changing during storage. It is preferable to use one having That is, when the hydrolyzable silyl group of the organic polymer (A) is an ethoxysilyl group, the silane coupling agent also has an ethoxysilyl group structure, and the hydrolyzable silyl group of the organic polymer (A) is isopropeno. In the case of a xylyl group, it is preferable to select a silane coupling agent having an isopropenoxysilyl group structure.

  Moreover, also in a silane coupling agent, it is preferable not to use the silane coupling agent which has a methyldimethoxysilyl group or a trimethoxysilyl group which discharge | releases methanol with a hydrolysis reaction. On the other hand, a silane coupling agent having a methyldiethoxysilyl group or a triethoxysilyl group is preferable because it releases highly safe ethanol.

  A silane coupling agent may mix | blend only 1 type, when you mix | blend with an adhesive composition, and may mix | blend multiple types in combination. When the silane coupling agent is added, the addition amount is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the organic polymer (A). 7 parts by weight is particularly preferred. When the compounding quantity of a silane coupling agent is less than 0.01 weight part, there exists a tendency for the storage stability of adhesive composition to be inferior, and there exists a tendency for the adhesiveness of the hardened | cured material obtained to be inferior. On the other hand, if the blending amount exceeds 20 parts by weight, there is a tendency that practical deep part curability cannot be obtained.

  Moreover, when producing a one-component adhesive composition, in order to have better storage stability, a titanium catalyst (B) and a silane coupling agent previously mixed and heat cured are used. It is preferable. In particular, when a titanium catalyst (B) and a silane coupling agent (D) having an epoxy group are mixed in advance and heat cured, an adhesive composition having both adhesiveness and storage stability can be obtained. To more preferable.

  In the adhesive composition of the present invention, for example, an epoxy resin, a phenol resin, sulfur, an alkyl titanate, an aromatic polyisocyanate, or the like is added in order to give an adhesive effect. Only one kind of these may be added, or a plurality of kinds may be added in combination.

  In the adhesive composition of the present invention, a filler is added as necessary. The filler is not particularly limited. For example, reinforcing filler such as fume silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate , Colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass micro Examples include balloons, organic microballoons of phenolic resins and vinylidene chloride resins, organic powders such as PVC powder and PMMA powder; and fibrous fillers such as asbestos, glass fibers and filaments.

  When adding a filler, the addition amount is preferably 1 to 250 parts by weight, more preferably 10 to 200 parts by weight, based on 100 parts by weight of the organic polymer of the component (A).

  When used in a one-component adhesive composition, in order to obtain good storage stability, the filler is used as a dehydrating agent such as calcium oxide as disclosed in JP-A No. 2001-181532. After uniformly mixing, it is preferable to add after enclosing in a bag made of an airtight material, leaving it to stand for an appropriate period of time and dehydrating and drying in advance.

  In addition, when the obtained cured product is used for an application requiring transparency, the added filler is a polymer made of a polymer such as methyl methacrylate disclosed in JP-A-11-302527. Powder, amorphous silica and the like are preferable, and hydrophobic silica and the like disclosed in JP-A No. 2000-38560 are more preferable.

  Here, hydrophobic silica is defined as (-SiO-hydrophobic group) by treating the surface of silicon dioxide fine powder generally occupied by silanol groups (-SiOH) with organosilicon halides or alcohols. Say things. Hydrophobic silica is not particularly limited, and for example, silanol groups present on the surface of fine silicon dioxide powder were treated with dimethylsiloxane, hexamethyldisilazane, dimethyldichlorosilane, trimethoxyoctylsilane, trimethylsilane, and the like. Things can be raised. The untreated silicon dioxide fine powder whose surface is occupied by silanol groups (—SiOH) is called hydrophilic silica fine powder.

  Further, when the obtained cured product is used for an application where high strength is required, the filler to be added includes fume silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, Silicon compounds such as hydrous silicic acid; carbon black, surface-treated fine calcium carbonate, calcined clay, clay, activated zinc white and the like are preferable, and the addition amount is 1 to 200 parts by weight with respect to 100 parts by weight of the organic polymer (A). Is preferred.

  Further, when the obtained cured product is used for an application requiring low strength and high elongation, the added filler is titanium oxide and calcium carbonate such as heavy calcium carbonate, magnesium carbonate, talc. , Ferric oxide, zinc oxide, shirasu balloon and the like are preferable, and the addition amount is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the organic polymer as the component (A).

  In addition, when adding calcium carbonate, the tendency for improvement in breaking strength, breaking elongation, and adhesiveness of a cured product obtained as the specific surface area increases is increased. One type of these fillers may be added, or a plurality of types may be added in combination.

  As an example of adding a plurality of additives, it is not particularly limited, and the combined use of calcium carbonate having a large particle size such as surface-treated fine calcium carbonate and heavy calcium carbonate has excellent physical properties of the obtained cured product. This is preferable.

  As the surface-treated fine calcium carbonate, those having a particle diameter of 0.5 μm or less and the particle surface being treated with a fatty acid or a fatty acid salt are preferable.

  Moreover, as calcium carbonate with a large particle size, the particle size is preferably 1 μm or more and the particle surface is not treated.

  When workability (such as sharpness) is required as the adhesive composition, or when the surface of the obtained cured product is required to be matte, the filler added is preferably an organic balloon or an inorganic balloon. These fillers may be added with or without surface treatment, and only one kind may be added, or a plurality of fillers may be mixed and added. The particle diameter of the balloon is preferably 0.1 mm or less for the purpose of improving workability (such as sharpness), and preferably 5 to 300 μm for the purpose of matting the surface of the cured product.

  The adhesive composition of the present invention is suitable for ceramics and other siding boards, housing outer wall joints and sealing materials for outer wall tiles, adhesives, etc., because the resulting cured product has excellent chemical resistance. used.

  When used in such applications, the resulting cured product is present in a portion that appears on the surface, such as a joint portion, so it is desirable that the design of the outer wall and the design of the cured product be harmonized. Particularly in recent years, high-quality outer walls such as sputter coating and colored aggregates have been used, and the importance of the design of the cured product has increased.

  In order to obtain a high-quality design, a scaly or granular substance is added to the adhesive composition of the present invention. Here, when a granular substance is added, the surface becomes sandy or sandstone-like rough, and when a scaly substance is added, it becomes an uneven surface due to scaly.

  In addition, since the obtained hardened | cured material is in harmony with a high-quality outer wall and is excellent in chemical resistance, the appearance with a high-class feeling has the characteristic of lasting for a long time.

  The scale-like or granular substance is not particularly limited, and examples thereof include those disclosed in JP-A-9-53063. The diameter is appropriately selected according to the material and pattern of the outer wall, but is 0.1 mm. The above is preferable. 0.1 to 5.0 mm is more preferable. In the case of a scaly substance, the thickness is preferably 1/10 to 1/5 (0.01 to 1.00 mm) of the diameter.

  The addition amount of the scaly or granular substance is appropriately selected depending on the size of the scaly or granular substance, the material of the outer wall, the pattern, etc., but is 1 to 200 weights with respect to 100 parts by weight of the adhesive composition. Part is preferred.

  The material of the scale-like or granular substance is not particularly limited, and examples thereof include natural products such as silica sand and mica, and inorganic materials such as synthetic rubber, synthetic resin, and alumina. These may be appropriately colored in accordance with the material, pattern, etc. of the outer wall in order to enhance the designability when filling the joints.

  A preferable finishing method is disclosed in JP-A-9-53063.

  The scaly or granular substance may be mixed in advance in the adhesive composition, or may be mixed with the adhesive composition at the time of use.

  For the same purpose, a balloon (preferably having an average particle size of 0.1 mm or more) can be added to the adhesive composition, and the resulting hardener has a sanding tone or sandstone tone. It becomes a certain surface and can achieve weight reduction. The balloon is a spherical filler with a hollow inside.

  The balloon is not particularly limited, and for example, JP-A-10-251618, JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A-7-113073. , JP-A-9-53063, JP-A-2000-154368, JP-A-2001-164237, WO97 / 05201, and the like.

  Examples of the material of the balloon include inorganic materials such as glass, shirasu, and silica; organic materials such as phenol resin, urea resin, polystyrene, and saran. In addition, a composite material of an inorganic material and an organic material; a laminated material including a plurality of layers can be given. These may use only 1 type and may add in combination of multiple types.

  In addition, as balloons, those whose surfaces are coated and those treated with various surface treatment agents can be used, and as specific examples, organic balloons are made of calcium carbonate, talc, titanium oxide or the like. Examples thereof include a coated one, and a surface treatment of an inorganic balloon with an adhesion-imparting agent.

  Furthermore, the particle size of the balloon is preferably 0.1 mm or more, more preferably 0.2 mm to 5.0 mm, and particularly preferably 0.5 mm to 5.0 mm. If it is less than 0.1 mm, even if it is added in a large amount, only the viscosity of the composition is increased, and the obtained cured product may not exhibit a rough feeling.

  In the case of adding a balloon, the amount added can be appropriately selected depending on the intended design, but a volume concentration of 5 to 25 vol% in the adhesive composition is used when the particle size is 0.1 mm or more. It is preferable to add so that it may become, and it is more preferable to add so that it may become 8-22 vol%. When the volume concentration of the balloon is less than 5 vol%, the feeling of roughness tends to be lost, and when it exceeds 25 vol%, the viscosity of the adhesive composition tends to increase and workability tends to deteriorate. Moreover, the modulus of the cured product obtained is increased, and the basic performance of the adhesive tends to be impaired.

  When adding the balloon, the anti-slip agent as disclosed in JP-A-2000-154368, the surface of the resulting cured product as disclosed in JP-A-2001-164237 is added, It is possible to add an amine compound or the like having a matte shape in combination. The amine compound is preferably a primary and / or secondary amine having a melting point of 35 ° C. or higher.

  In addition, as a balloon, the thermally expansible fine particle hollow body currently disclosed by Unexamined-Japanese-Patent No. 2004-51701, 2004-66749, etc. can also be used. The thermally expandable fine hollow body is a polymer outer shell material (vinylidene chloride copolymer, acrylonitrile copolymer, or vinylidene chloride-acrylonitrile copolymer weight) such as a hydrocarbon having 1 to 5 carbon atoms. It is a plastic sphere wrapped in a spherical shape.

  By adding the thermally expandable fine hollow body to the adhesive composition of the present invention, it can be easily peeled off without destroying the adherend when it becomes unnecessary, and the organic solvent. An adhesive composition that can be removed by heating without using any is obtained. This is because the gas pressure in the shell of the thermally expandable fine hollow body increases by heating the adhesive part, and the polymer outer shell material softens and expands dramatically, thereby peeling the adhesive interface. .

  A silicate is added to the adhesive composition of the present invention as necessary. The silicate acts as a crosslinking agent for the organic polymer (A), and as a result, has a function of improving the restorability, durability, and creep resistance of the resulting cured product. Further, by adding silicate, the obtained cured product is improved in adhesion and water-resistant adhesion and adhesion durability under high temperature and high humidity.

  The silicate is not particularly limited, and examples thereof include tetraalkoxysilane or a partial hydrolysis condensate thereof. More specifically, tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxy Tetraalkoxysilanes (tetraalkyl silicates) such as triethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, and , And their partial hydrolysis condensates.

  When adding silicate, 0.1-20 weight part is preferable with respect to 100 weight part of organic polymers (A), and, as for the addition amount, 0.5-10 weight part is more preferable.

  The partially hydrolyzed condensate of tetraalkoxysilane is not particularly limited, and examples thereof include a product obtained by adding water to tetraalkoxysilane and partially hydrolyzing and condensing it.

  It is preferable to add a partially hydrolyzed condensate of tetraalkoxysilane because the effect of improving the restorability, durability, and creep resistance of the resulting cured product is greater than the adhesive composition to which tetraalkoxysilane is added. .

  As the partial hydrolysis-condensation product of tetraalkoxysilane, for example, methyl silicate 51, ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.) and the like are commercially available, and these can be used as additives.

  When the silicate is added, it has a hydrolyzable group having the same structure as the hydrolyzable group of the organic polymer (A) for the purpose of preventing the curability of the adhesive composition from changing during storage. Is preferably used. That is, when the hydrolyzable silyl group of the organic polymer (A) is an ethoxysilyl group, the silicate having the ethoxysilyl group is converted to an isopropyl group having an isopropenoxysilyl group. In some cases, it is preferable to select a silicate having an isopropoxysilyl group.

  In addition, it is preferable not to use a silicate having a methoxysilyl group that releases methanol with a hydrolysis reaction. On the other hand, a silicate having an ethoxysilyl group is preferable because it releases highly safe ethanol.

  If necessary, a tackifier is added to the adhesive composition of the present invention. The tackifying resin is not particularly limited as long as it is normally used regardless of whether it is solid or liquid at room temperature. For example, a styrene block copolymer, a hydrogenated product thereof, a phenol resin, a modified phenol resin (For example, cashew oil-modified phenol resin, tall oil-modified phenol resin, etc.), terpene phenol resin, xylene-phenol resin, cyclopentadiene-phenol resin, coumarone indene resin, rosin resin, rosin ester Resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.) , Hydrogenated petroleum resin, terpene resin, DCPD resin petroleum resin and the like. Only one kind of these may be added, or a plurality of kinds may be added in combination.

  The styrenic block copolymer and its hydrogenated product are not particularly limited. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene. Examples include butylene-styrene block copolymer (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), and styrene-isobutylene-styrene block copolymer (SIBS).

  When the tackifier is added, the addition amount is preferably 5 to 1,000 parts by weight, more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the organic polymer (A).

  If necessary, a solvent or a diluent is added to the adhesive composition of the present invention. Solvents and diluents are not particularly limited. For example, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers Etc. Only one kind of these may be added, or a plurality of kinds may be added in combination.

  When adding a solvent or diluent, the boiling point of the solvent or diluent is preferably 150 ° C. or higher, preferably 200 ° C. or higher, in order to prevent the diffusion of volatile components into the air when the adhesive composition is used indoors. Is more preferable.

  In the adhesive composition of the present invention, a physical property modifier is added as necessary. The physical property modifier has a function of adjusting the tensile properties and hardness of the cured product to be produced.

  The physical property modifier is not particularly limited, and examples thereof include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropeno Alkyl isopropenoxy silanes such as xy silane and γ-glycidoxy propyl methyl diisopropenoxy silane; γ-glycidoxy propyl methyl dimethoxy silane, γ-glycidoxy propyl trimethoxy silane, vinyl trimethoxy silane, vinyl dimethyl Methoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxy Alkoxysilanes having a functional group of the run and the like; silicone varnishes; polysiloxanes and the like. Only one kind of these may be added, or a plurality of kinds may be added in combination.

  Among the physical property modifiers, those that produce a compound having a monovalent silanol group in the molecule by hydrolysis are preferred because they have an effect of reducing the modulus without deteriorating the stickiness of the surface of the resulting cured product. Among these, those that generate trimethylsilanol by hydrolysis are more preferable.

The compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis is not particularly limited. For example, compounds disclosed in JP-A-5-117521, and alkyls such as hexanol, octanol, decanol, etc. Derivatives of alcohols, compounds that produce an organosilicon compound represented by R ₃ SiOH such as trimethylsilanol by hydrolysis, trimethylolpropane, glycerin, pentaerythritol or sorbitol disclosed in JP-A-11-241029 And the like, which are derivatives of polyhydric alcohols having 3 or more hydroxyl groups in one molecule, such as trimethylsilanol, which produce an organosilicon compound represented by R ₃ SiOH by hydrolysis.

Further, it is a derivative of an oxypropylene polymer disclosed in JP-A-7-258534, which produces an organosilicon compound represented by R ₃ SiOH such as trimethylsilanol by hydrolysis, and further JP-A-6-279893. And a group having a silicon group capable of forming a compound having a monovalent silanol group by hydrolysis, and a group having a crosslinkable hydrolyzable silicon disclosed in the above-mentioned issue.

  When adding a physical property modifier, the addition amount is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the organic polymer (A). 0.5-10 weight part is more preferable.

  When adding a physical property modifier, a hydrolyzable group having the same structure as the hydrolyzable group of the organic polymer (A) is used for the purpose of preventing the curability of the adhesive composition from changing during storage. It is preferable to use what has. That is, when the hydrolyzable silyl group of the organic polymer (A) is an ethoxysilyl group, the physical property modifier having an ethoxysilyl group is used, and the hydrolyzable silyl group of the organic polymer (A) is isopropenoxysilyl. When it is a group, it is preferable to select a physical property modifier having an isopropoxysilyl group.

  Moreover, it is preferable not to use the physical property modifier which has a methoxysilyl group which releases methanol with a hydrolysis reaction also in a physical property modifier. On the other hand, a physical property modifier having an ethoxysilyl group is preferable because it releases highly safe ethanol.

  In the adhesive composition of the present invention, a thixotropic agent (anti-sagging agent) is added as necessary. The thixotropy imparting agent refers to an agent having a function of preventing dripping of the adhesive composition and improving workability.

  The thixotropic agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Further, rubber powder having a particle size of 10 to 500 μm disclosed in JP-A No. 11-349916 and organic fibers disclosed in JP-A No. 2003-155389 are exemplified. One of these thixotropic agents (anti-sagging agents) may be added, or a plurality of them may be added in combination.

  When the thixotropic agent is added, the addition amount is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the organic polymer (A).

  In the adhesive composition of this invention, the compound which has an epoxy group in 1 molecule is added as needed. By adding a compound having an epoxy group, the restorability of the obtained cured product can be enhanced.

  The compound having an epoxy group is not particularly limited, and examples thereof include epoxidized unsaturated fats and oils; epoxidized unsaturated fatty acid esters; alicyclic epoxy compounds; compounds such as epichlorohydrin derivatives; It is done. More specifically, epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate And epoxybutyl stearate. Among these, E-PS is preferable.

  A photocurable material is added to the adhesive composition of the present invention as necessary. The photo-curing substance is a substance in which the molecular structure undergoes a chemical change in a short time by the action of light, resulting in a change in physical properties such as curing. When a photocurable substance is added to the adhesive composition, a film of the photocurable substance is formed on the surface of the resulting cured product, and the stickiness and weather resistance of the cured product are improved.

  The photocurable material is not particularly limited, and examples thereof include organic monomers, oligomers, resins, and compositions containing them, such as unsaturated acrylic compounds, polyvinyl cinnamates, or azidation. Examples thereof include resins.

  Examples of the unsaturated acrylic compound include monomers, oligomers or mixtures thereof having one or more acrylic or methacrylic unsaturated groups in one molecule. Specific examples thereof include propylene (or butylene, ethylene, and the like). ) Monomers such as glycol di (meth) acrylate and neopentyl glycol di (meth) acrylate or oligoesters having a molecular weight of 10,000 or less. More specifically, for example, a special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; M-305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (Multifunctional) Aronix M-400 (all Aronix made by Toa Gosei Co., Ltd.) ) Etc. Among these, a compound having an acrylic functional group is preferable, and a compound having an average of 3 or more acrylic functional groups in one molecule is more preferable.

  Examples of the polyvinyl cinnamate include a photosensitive resin having a cinnamoyl group as a photosensitive group, a compound obtained by esterifying polyvinyl alcohol with cinnamic acid, and many other polyvinyl cinnamate derivatives.

  The azide resin is known as a photosensitive resin having an azido group as a photosensitive group. Usually, in addition to a rubber photosensitive solution in which a diazide compound is added as a photosensitive agent, a “photosensitive resin” (March 17, 1972). (Nippon Publishing, Publishing Society of Printing Press, page 93-, page 106-, page 117-), there are detailed examples. These are used alone or in combination, and a sensitizer is added as necessary. be able to.

  Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect.

  When adding a photocurable substance, the addition amount is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the organic polymer (A). 0.5-10 weight part is more preferable. If it is 0.1 parts by weight or less, there is almost no effect of improving the weather resistance of the obtained cured product, and if it is 20 parts by weight or more, the obtained cured product tends to be too hard and cracks and the like tend to occur.

  An oxygen curable substance is added to the adhesive composition of the present invention as necessary. An oxygen curable substance can be cured by reacting with oxygen in the air. By adding an oxygen curable substance, a cured film is formed near the surface of the resulting cured product, and the surface of the cured product becomes sticky. And can prevent adhesion of dust and dust.

  The oxygen curable substance is not particularly limited as long as it is a compound having an unsaturated compound capable of reacting with oxygen in the air. For example, dry oil such as drill oil and linseed oil, and various types obtained by modifying the compound Alkyd resin; acrylic polymer modified with drying oil, epoxy resin, silicone resin; obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene and 1,3-pentadiene -Liquid polymers such as polybutadiene, 1,4-polybutadiene, and C5-C8 diene polymers; vinyl compounds such as acrylonitrile and styrene copolymerizable with these diene compounds, diene compounds, and diene compounds. Liquid copolymers such as NBR and SBR obtained by copolymerization so as to be the main component, and various modified products thereof (male Emissions modifications thereof, boiled oil-modified, etc.) and the like. Of these, drill oil and liquid diene polymers are preferred. Only one kind of oxygen curable substance may be added, or a plurality of kinds may be added in combination.

  Note that the effect of the oxygen curable substance may be enhanced by adding a catalyst or a metal dryer that accelerates the curing reaction. The catalyst and the metal dryer that accelerate the curing reaction are not particularly limited, and examples thereof include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate, and amine compounds. .

  When the oxygen curable substance is added, the addition amount is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the organic polymer (A). 0.5-10 weight part is more preferable. When the amount added is less than 0.1 parts by weight, the resulting cured product has a tendency to improve the stain resistance, and when it exceeds 20 parts by weight, the tensile properties of the resulting cured product tend to be impaired.

  Further, the oxygen curable substance is preferably mixed with a photocurable substance as disclosed in JP-A-3-160053.

  An antioxidant is added to the adhesive composition of the present invention as necessary. By adding an antioxidant, the heat resistance of the resulting cured product can be increased.

  The antioxidant is not particularly limited, and examples thereof include hindered phenol type, monophenol type, bisphenol type, and polyphenol type antioxidants. Of these, hindered phenol antioxidants are preferred. Tinuvin 622LD, Tinuvin 144; CHIMASSORB 944LD, CHIMASSORB 119FL (all manufactured by Ciba Specialty Chemicals Co., Ltd.); (All are manufactured by ADEKA Corp.); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all are Sankyo Life Tech Co., Ltd.) Hindered amine light stabilizers such as (manufactured) are also preferred. Specific examples of the antioxidant are also disclosed in JP-A-4-283259 and JP-A-9-194731.

  When adding antioxidant, 0.1-10 weight part is preferable with respect to 100 weight part of organic polymers (A), and, as for the addition amount, 0.2-5 weight part is more preferable.

  If necessary, a light stabilizer is added to the adhesive composition of the present invention. Addition of the light stabilizer can prevent photooxidation deterioration of the obtained cured product.

  The light stabilizer is not particularly limited, and examples thereof include benzotriazole-based, hindered amine-based, and benzoate-based compounds. Among these, hindered amine light stabilizers are preferable.

  When adding a light stabilizer, the addition amount is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the organic polymer (A). 0.2-5 weight part is more preferable. Specific examples of the light stabilizer are also disclosed in JP-A-9-194731.

  When a photocurable material such as an unsaturated acrylic compound is added to the adhesive composition of the present invention, a hindered amine light stabilizer having a tertiary amine group is added as disclosed in JP-A-5-70531. The addition is more preferable because the storage stability of the adhesive composition is improved.

  The hindered amine light stabilizer having a tertiary amine group is not particularly limited. For example, Tinuvin 622LD, Tinuvin 144, CHIMASSORB119FL (all of which are manufactured by Ciba Specialty Chemicals); ADK STAB LA-57, LA- 62, LA-67, LA-63 (all manufactured by ADEKA Corporation); Sanol LS-765, LS-292, LS-2626, LS-1114, LS-744 (all of these are Sankyo Lifetech Co., Ltd.) Manufactured).

  An ultraviolet absorber is added to the adhesive composition of the present invention as necessary. By adding the ultraviolet absorber, the surface weather resistance of the obtained cured product is improved.

  The ultraviolet absorber is not particularly limited, and examples thereof include benzophenone series, benzotriazole series, salicylate series, substituted tolyl series, and metal chelate series compounds. Of these, benzotriazole ultraviolet absorbers are preferred.

  When adding an ultraviolet absorber, the addition amount is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the organic polymer (A). 0.2-5 weight part is more preferable.

  The antioxidant, light stabilizer and ultraviolet absorber are preferably added together in the adhesive composition. For example, phenolic or hindered phenolic antioxidants, hindered amine light stabilizers and benzotriazole ultraviolet rays. It is preferable to mix and add the absorbent.

  An epoxy resin is added to the adhesive composition of the present invention as necessary. Addition of the epoxy resin improves the adhesiveness of the obtained cured product, and the adhesive composition to which the epoxy resin is added is preferably used as an adhesive, particularly as an adhesive for exterior wall tiles.

  The epoxy resin is not particularly limited, for example, epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant epoxy resin such as tetrabromobisphenol A glycidyl ether, novolak type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various Alicyclic epoxy resin, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkyleneglycol Diglycidyl ether, glycidyl ethers of polyhydric alcohols such as glycerin, hydantoin type epoxy resins, such as epoxidized unsaturated polymer such as petroleum resins.

  Among these, those having at least two epoxy groups in one molecule are preferable because they increase the reactivity of the adhesive composition and the obtained cured product easily forms a three-dimensional network structure. Type epoxy resin or novolac type epoxy resin is more preferable.

  When adding an epoxy resin, the amount of addition varies depending on the use application of the adhesive composition, for example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of the cured epoxy resin, It is preferable to add 1 to 100 parts by weight of the organic polymer (A) with respect to 100 parts by weight of the epoxy resin, and it is more preferable to add 5 to 100 parts by weight. On the other hand, when improving the intensity | strength of the hardened | cured material of an organic polymer (A), it is preferable to add 1-200 weight part of epoxy resins with respect to 100 weight part of organic polymers (A), and 5-100 weight. It is more preferable to add part.

  When an epoxy resin is added to the adhesive composition of the present invention, it is preferable to add a curing agent for the epoxy resin.

  The curing agent for the epoxy resin is not particularly limited as long as it is a compound having a function of curing the epoxy resin. For example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylidine. Primary and secondary amines such as range amine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated polyether; 2,4,6-tris (dimethylaminomethyl) phenol, tripropylamine, etc. Tertiary amines and salts of these tertiary amines; polyamide resins; imidazoles; dicyandiamides; boron trifluoride complex compounds; phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl anhydride , Pyromellitic acid anhydride, carboxylic acids such as anhydrous Kuroren acid; alcohols; phenols; carboxylic acids; compounds of diketone complex compounds of aluminum or zirconium are exemplified. Only one kind of these may be added, or a plurality of kinds may be added in combination.

  The addition amount of the epoxy resin curing agent is preferably 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.

  Among the curing agents for epoxy resins, it is preferable to use a ketimine compound because a one-component curing composition is obtained. The ketimine compound exists stably in the absence of moisture, and is decomposed into a primary amine and a ketone by moisture, and the resulting primary amine becomes a room temperature curable curing agent for the epoxy resin. Examples of the ketimine compound include compounds obtained by a condensation reaction between an amine compound and a carbonyl compound.

  The amine compound and carbonyl compound used in the production of the ketimine compound are not particularly limited and include known compounds. Examples of the amine compound include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3- Diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, p, p'-biphenylenediamine and other diamines; 1,2,3-triamino Polyamines such as propane, triaminobenzene, tris (2-aminoethyl) amine, tetrakis (aminomethyl) methane; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine; polyoxyalkyl Polysilanes; aminosilanes such as γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane; Etc.

  Examples of the carbonyl compound include aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone and trimethylcyclohexanone; acetone , Aliphatic ketones such as methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone; acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate , Β-dicarbonyl compounds such as diethyl malonate, methyl ethyl malonate, dibenzoylmethane And the like.

  Ketimine compounds having an imino group include those obtained by reacting an imino group with styrene oxide; glycidyl ethers such as butyl glycidyl ether and allyl glycidyl ether; glycidyl esters and the like.

  These ketimine compounds may be added alone or in combination of two or more.

  When the ketimine compound is added, the amount added varies depending on the types of the epoxy resin and ketimine, but is usually preferably 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin.

  A flame retardant is added to the adhesive composition of the present invention as necessary. It does not specifically limit as a flame retardant, For example, flame retardants, such as phosphorus flame retardants, such as ammonium polyphosphate and tricresyl phosphate; Aluminum hydroxide, magnesium hydroxide, and thermally expansible graphite can be added. Only one type of flame retardant may be added, or multiple types may be added in combination.

  When adding a flame retardant, as the addition amount, 5-200 weight part is preferable with respect to 100 weight part of organic polymers (A), and 10-100 weight part is more preferable.

  In the adhesive composition of the present invention, various additives other than those described above are added as necessary for the purpose of adjusting various physical properties of the adhesive composition or the cured product obtained. Such additives include, for example, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposing agents, lubricants, pigments, foaming agents, anti-anticides, Examples include fungicides. Specific examples of these are disclosed in JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, JP-A-2001-72854, and the like. ing. Moreover, these additives may add only 1 type and may add it in combination of multiple types.

  When the adhesive composition is a one-pack type, since all the blending components are blended in advance, if moisture exists in the blend, curing may proceed during storage. Therefore, it is preferable to add a water-containing blending component after dehydrating and drying in advance, or dewatering by decompression or the like during blending and kneading.

  When the adhesive composition is a two-component type, it is not necessary to add a curing catalyst to the main agent containing an organic polymer having a reactive silicon group, so that the progress of curing is possible even if the composition contains a small amount of moisture. Although there is little concern about (gelation), when long-term storage stability is required, it is preferable to dehydrate and dry.

  As the dehydration and drying method, use heat drying method or vacuum dehydration method when the compound is a solid such as powder, and use vacuum zeolite dehydration method or synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide, etc. The dehydration method is preferred. Furthermore, n-propyltrimethoxysilane, n-propyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltriisopropenoxysilane, phenyltriacetoxysilane, vinyltrimethoxysilane, vinyl Methyldimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltriisopropenoxysilane, vinyltriacetoxysilane, methylsilicate, ethylsilicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane; 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazoly Oxazolidine compounds such emissions; or, with the addition of the isocyanate compound in the adhesive composition, the dehydration method is performed by reacting with the water contained in the formulation is also preferable. Thus, the storage stability of the adhesive composition is improved by the addition of the alkoxysilane compound, the oxazolidine compound, and the isocyanate compound.

  Among these, since the storage stability of the adhesive composition is better, an alkoxysilane compound is preferable, and phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropenoxysilane, phenyltriacetoxysilane, vinyltrimethoxy Silane, vinyltriethoxysilane, and vinyltriisopropenoxysilane are more preferable, and phenyltriethoxysilane is particularly preferable.

  When the alkoxysilane compound is added, a hydrolyzable group having the same structure as the hydrolyzable group of the organic polymer (A) is used for the purpose of preventing the curability of the adhesive composition from changing during storage. It is preferable to use what has. That is, when the hydrolyzable silyl group of the organic polymer (A) is an ethoxysilyl group, the alkoxysilane compound also has an ethoxysilyl group structure, and the hydrolyzable silyl group of the organic polymer (A) is isopropenoxy. When it is a silyl group, it is preferable to select an alkoxysilane compound having an isopropenoxysilyl group structure.

  Moreover, it is preferable not to use the alkoxysilane compound which has a methoxysilyl group which releases methanol with a hydrolysis reaction also in an alkoxysilane compound. On the other hand, an alkoxysilane compound having an ethoxysilyl group is preferable because it releases highly safe ethanol.

  As an addition amount when using an alkoxysilane compound for the purpose of drying, 0.1 to 20 parts by weight is preferable with respect to 100 parts by weight of the organic polymer (A). 0.5-10 weight part is more preferable.

  The method for preparing the adhesive composition of the present invention is not particularly limited. For example, the above-described blending components are prepared and kneaded at room temperature or under heat using a mixer, roll, kneader, or the like, and a suitable solvent is used. A known method such as a method in which a small amount is used and the compounding components are dissolved and then mixed can be employed.

  When exposed to the atmosphere, the adhesive composition of the present invention forms a three-dimensional network structure by the action of moisture, and cures to a solid having rubbery elasticity. The cured product obtained by curing the adhesive composition of the present invention preferably has a large tensile stress. Specifically, the adhesive composition is formed into a sheet having a thickness of 3 mm, placed under conditions of 23 ° C. and 50% RH for 3 days, further cured at 50 ° C. for 4 days, and punched into a dumbbell-shaped No. 3 shape. After that, the 50% tensile stress when measured according to JIS K 6251 is preferably 0.3 MPa to 5 MPa, more preferably 0.5 MPa to 4 MPa, and 0.7 MPa to 3 MPa. It is more preferable that the pressure is 1 MPa to 2 MPa.

  Moreover, it is preferable that the hardened | cured material obtained by hardening the adhesive composition of this invention has high hardness. Specifically, a cured product is prepared so as to have a diameter of 4 cm and a thickness of 1.5 cm under a condition of 23 ° C. and 50% RH, and the center of the cured product obtained by curing for 7 days is defined in JIS K 6253. The hardness when measured with a durometer type A in conformity is preferably A10 to A100, more preferably A20 to A90, still more preferably A30 to A80, and A40 to A70. Particularly preferred.

  When the base material and the base material are bonded using an adhesive that gives a soft hardened product having a 50% tensile stress of less than 0.3 MPa or a hardness of less than A10, the resulting cured product will have a gap between the substrates when force is applied. There is a tendency to cause a problem of shifting. In addition, an organic polymer having a high molecular weight is usually used as an adhesive that gives a soft cured product, which tends to cause problems such as poor workability or inability to obtain practical curability. On the other hand, when the base material and the base material are bonded using an adhesive that gives a hardened product that has a 50% tensile stress exceeding 5 MPa or a hardness exceeding A100, There is a tendency that the base material peels off badly, or that the base material breaks when force is applied.

  The adhesive composition of the present invention is suitably used as an adhesive for interior use because of its high safety. Further, it can be used for various applications such as elastic adhesives; contact-type adhesives; spray-type sealing materials; crack repair materials; Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin molding, etc. alone or with the help of a primer, it can be used as various types of adhesive compositions.

  In addition, the adhesive composition of the present invention is an interior panel adhesive, a tile adhesive, a stone adhesive, a ceiling finish adhesive, a floor finish adhesive, a wall finish adhesive, and a vehicle panel adhesive. It can also be used as adhesives, adhesives for assembly of electrical / electronic / precision equipment, sealing materials for direct glazing, sealing materials for double-glazed glass, sealing materials for SSG construction methods, or sealing materials for working joints in buildings. .

  Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1
Deethanol-free organic polymer A-1 (number average molecular weight of about 26,000 (Tosoh HLC-8120GPC was used as the liquid feeding system, Tosoh TSK-GEL H type was used as the solvent, and the solvent was measured using THF). (Polystyrene-converted molecular weight) and trifunctional polyoxypropylene polymer having a triethoxysilyl group at the end) 100 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., trade name: Hakujyuka CCR) 100 parts by weight, heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: Whiten SB) 150 parts by weight, diisodecyl phthalate plasticizer (manufactured by Jay Plus Co., Ltd., trade name: DIDP) 50 parts by weight, Anti-sagging agent (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon 6500) 3 parts by weight, salicylate UV absorber (Sumitomo 1 part by weight, manufactured by Kagaku Co., Ltd., trade name: Sumisorb 400) and 1 part by weight of a hindered amine light stabilizer (manufactured by Sankyo Lifetech Co., Ltd., trade name: Sanol LS-765) are mixed and kneaded thoroughly. After that, it was dispersed by passing three times through three paint rolls. Thereafter, dehydration under reduced pressure is performed at 120 ° C. for 2 hours, and after cooling to 50 ° C. or less, 2.5 parts by weight of vinyltriethoxysilane (product name: A-151, manufactured by Momentive Co., Ltd.), an adhesion-imparting agent Γ- (2-aminoethyl) aminopropyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name: KBE-603) 3.5 parts by weight, titanium diisopropoxide bis (ethylacetoacetate) (as titanium catalyst) DuPont Co., Ltd., trade name: Tyzer PITA) 4 parts by weight are added and kneaded, kneaded in a substantially water-free state, and then sealed in a cartridge which is a moisture-proof container. A composition was obtained.

(Examples 2 to 16) and (Comparative Examples 1 to 4)
In the same manner as in Example 1, adjustments were made according to the compounding agents and compounding amounts shown in Table 1. The compounding agents used are shown below.
Deethanol-type organic polymer A-2: a bifunctional polyoxypropylene-based polymer having a number average molecular weight of about 15,300 and having a triethoxysilyl group at the terminal. Deethanol-free organic polymer A-3: number average Trifunctional polyoxypropylene-based polymer / demethanol-type organic polymer A-4 having a molecular weight of about 16,300 and having a triethoxysilyl group at the end: Number average molecular weight of about 15,300, and having a terminal end of trimethoxysilyl -Functional polyoxypropylene-based polymer / demethanol-type organic polymer A-5: a trifunctional polyoxypropylene-based polymer / silica sand having a number average molecular weight of about 16,300 and having a trimethoxysilyl group at the terminal No. 8: manufactured by Maruo Calcium Co., Ltd., silica sand / Hexamol DINCH: manufactured by BASF Co., Ltd. Nylester Novales L100: manufactured by Rutgers Chemical Co., Ltd., liquid hydrocarbon resin / tetraethyl orthosilicate: manufactured by Tokyo Chemical Industry Co., Ltd./KBE-103: manufactured by Shin-Etsu Silicone Co., Ltd., phenyltriethoxysilane / A-171: Momentive Co., Ltd., vinyltrimethoxysilane / KBE-403: Shin-Etsu Silicone Co., Ltd., γ-glycidoxypropyltriethoxysilane / A-187: Momentive Co., Ltd., γ-glycidoxypropyltrimethoxy Silane Tizer TPT: DuPont, Titanium Tetraisopropoxide, Titanium Tetraethoxide: Tokyo Chemical Industry Co., Ltd. Neostan U220H: Nitto Kasei Co., Dibutyltin Bis (acetylacetonate)
S-1: manufactured by Nitto Kasei Co., Ltd., siloxy group-containing dioctyltin compound

(safety)
In the above-mentioned adhesive composition, A that does not use a demethanol-type organic polymer or an organic tin-based catalyst, A that uses a demethanol-type organic polymer and does not use an organic tin-based catalyst, and B A product using an organotin catalyst without using a methanol-type organic polymer was designated as C. It can be said that the adhesive composition A is higher in safety than the adhesive compositions B and C.

(Surface curing time)
Under conditions of 23 ° C. and 50% RH, the adhesive composition is stretched with a spatula so that the thickness is about 3 mm, and the surface of the adhesive composition is lightly touched over time using a microspatula. The time until contact with the microspatula was measured (surface hardening time before storage). Moreover, after storing the adhesive composition at 50 ° C. for 28 days, the curing time was measured by the same method as described above (surface curing time after storage) at 23 ° C. and 50% RH for 1 day.

(viscosity)
Under the conditions of 23 ° C. and 50% RH, the adhesive composition was BM type viscometer, rotor No. manufactured by Tokyo Keiki Co., Ltd. 7 was used to measure the 2 rpm viscosity (2 rpm viscosity before storage). Moreover, after storing the adhesive composition at 50 ° C. for 28 days, the adhesive composition was kept at 23 ° C. and 50% RH for 1 day, and the 2 rpm viscosity was measured in the same manner as described above (2 rpm viscosity after storage).

(Storage stability)
The change rate of the surface curing time after storage with respect to the surface cure time before storage, and the change rate of viscosity after storage with respect to the viscosity before storage were determined. It can be said that the closer the rate of change is to 100%, the better the storage stability.

(Adhesiveness)
On the surface of a slate plate (length: 100 mm, width: 25 mm, thickness: 4 mm) under the conditions of 23 ° C. and 50% RH, the adhesive composition was applied in a length of 25 mm, a width of 25 mm, and a thickness of 1 mm. A plywood (length 100 mm, width 25 mm, thickness 3 mm) was bonded to the substrate. This test piece was placed under conditions of 23 ° C. and 50% RH for 3 days, and further placed at 50 ° C. for 4 days for curing. Thereafter, based on JIS K 6850, a tensile test was performed at a tensile speed of 50 mm / min using an autograph manufactured by Shimadzu Corporation to measure the shear bond strength and the cohesive failure rate. The cohesive failure rate is determined by visually checking cohesive failure (destruction at the adhesive part) and interface failure (peeling at the interface between the adhesive and the substrate), and the area ratio of the part that is cohesive to the coated surface. Asked. It can be said that the higher the shear bond strength and the cohesive failure rate, the better the adhesiveness.

(50% tensile stress)
Under the conditions of 23 ° C. and 50% RH, the adhesive composition was formed into a sheet having a thickness of 3 mm for 3 days, and further cured at 50 ° C. for 4 days. In accordance with JIS K 6253, the cured product was punched into a dumbbell shape No. 3, and then a tensile test was performed at a tensile speed of 200 mm / min using an autograph manufactured by Shimadzu Corporation to measure 50% tensile stress. .

(hardness)
Under the condition of 23 ° C. and 50% RH, the surface of the adhesive composition was smoothed to have a diameter of 4 cm and a thickness of 1.5 cm, and a cured product was prepared and cured for 7 days. Thereafter, the hardness of the cured product was measured using a type A durometer of Kobunshi Keiki Co., Ltd. in accordance with JIS K 6253.

  As shown in Table 1, the examples do not contain a demethanol-type organic polymer or an organic tin-based catalyst, and therefore, compared with comparative examples including conventionally used demethanol-type organic polymers and organic tin-based catalysts. It turns out that safety is high. Furthermore, it can be put to practical use also in various physical properties such as curability, storage stability, adhesiveness, tensile stress, and hardness.

Claims (9)

(A) an organic polymer of trifunctional terminated with silicon-containing group capable of crosslinking by forming a siloxane bond, said silicon-containing groups Ri triethoxysilyl group der, main chain skeleton polyoxyalkylene the organic polymer having a number average molecular weight Ru system der is 3,000 to 20,000,
(B) a titanium catalyst,
Only contains, in compliance with JIS K 6253, a non-organotin adhesive composition for interior hardness in the case of measuring the cured product Type A durometer is A40～A90. The non-organic tin adhesive composition for interior use according to claim 1 , wherein the polyoxyalkylene polymer is a polyoxypropylene polymer. The titanium catalyst (B) has the general formula (3):
Ti (OR ³ ) ₄ (3)
(R ³ is an organic group, and four R ^{3 s} may be the same or different from each other.) And / or the general formula (4):
O = Ti (OR ³ ) ₂ (4)
(R ³ are the same. Above) a titanium catalyst represented by the non-organotin adhesive composition for interior according to claim 1 or 2. The titanium catalyst has the general formula (5):

(B R ^{4 's} are each independently a hydrocarbon group having 1 to 20 carbon atoms. (4-b) R ^{5' s} are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. (8-2b) pieces of R ⁶ are each independently a hydrocarbon group having 1 to 8 carbon atoms, or —OR ⁷ (R ⁷ is a hydrocarbon group having 1 to 8 carbon atoms). B is an integer of 0 to 3.), a titanium chelate catalyst represented by the general formula (6):

(R ⁵ and R ⁶ are the same as above. R ⁸ is a divalent hydrocarbon group having 1 to 20 carbon atoms.)
A titanium chelate catalyst represented by the general formula (7):

(Wherein R ⁵ and R ⁶ are the same as described above),
The non-organotin-based adhesive composition for interior use according to claim 3 , which is at least one selected from the group consisting of: Furthermore, a non-organotin adhesive composition for interior containing a plasticizer, 10 to 100 wt% of the plasticizer component is a non-phthalate plasticizer (C), according to claim 1-4 The non-organotin-based adhesive composition for interior according to any one of the above. The non-phthalate plasticizer (C) is cyclohexanedicarboxylic acid diester, alkylsulfonic acid phenyl ester is at least one selected from the group consisting of oligomers, consisting of an aromatic vinyl compound, according to claim 5 Non-organotin adhesive composition for interior use. Furthermore, the non-organotin-based adhesive composition for interior use according to any one of claims 1 to 6 , further comprising an epoxy group-containing silane coupling agent (D). In conformity with JIS K 6251, 50% tensile stress when the cured product was measured with No. 3 dumbbell test piece 3mm thick, it is 0.3MPa～5MPa, any one of claims 1-7 A non-organotin adhesive composition for interior use as described in 1. Hardened | cured material which hardened the non-organotin-type adhesive composition for interiors of any one of Claims 1-8 .