JPWO2006088112A1 - Reactive resin composition - Google Patents

Abstract

An object of the present invention is to provide an adhesive composition for difficult-to-adhere base materials that can provide sufficient adhesive strength to difficult-to-adhere difficult-to-adhere base materials, and an average of 0.8 or more per molecule. This is achieved by a reactive resin composition containing an organic polymer (A) having a reactive silicon group, a crosslinking regulator (B) catalyst (C), and a filler (D). As the crosslinking regulator (B), (Bi) a silicon compound having one Si atom in the molecule and one or two total hydroxyl groups and hydrolyzable groups bonded to the Si atom. (B-ii) The number of Si atoms in the molecule is 2 to 20, the total number of hydroxyl groups and hydrolyzable groups bonded to any Si atom in the molecule is 2 to 5, and each Si Examples include a silicon compound in which the total number of hydroxyl groups and hydrolyzable groups bonded to the same Si atom in the atom is 0 or 1, and (B-iii) a silicon compound of the following formula (1). R4-NH-R1-Si (R2) z (R3) 3-z (1)

Description

  The present invention relates to a reactive silicon group-containing organic polymer having an average of 0.8 or more silicon-containing functional groups (hereinafter also referred to as “reactive silicon groups”) forming a siloxane bond, and a crosslinking regulator. And a reactive resin composition containing a catalyst and a filler. The present invention also relates to an adhesive particularly suitable for conventionally known difficult-to-bond substrates such as polyolefin substrates.

  It is known that an organic polymer having a reactive silicon group in the molecule exhibits reactivity that the reactive silicon group is hydrolyzed by moisture to form a siloxane bond.

  Among these polymers having reactive silicon groups, polymers whose main chain is polyoxyalkylene and polymers whose main chain is polyisobutylene have already been industrially produced and are used as sealing materials, adhesives, injections Widely used in applications such as wood, putty and paint.

  For these applications, adhesion to various materials is required, and adhesion is imparted by adding an adhesion-imparting agent such as a silane coupling agent (Patent Document 1) or a titanium coupling agent (Patent Document 2). Has improved sex. Moreover, the epoxy resin (patent document 3) and the acrylic resin (patent document 4) compatible with the organic polymer which has a reactive silicon group were added, and the adhesiveness has been improved.

However, recyclable and safer materials such as polyolefin materials such as polyethylene, polypropylene, polyolefins such as ethylene propylene terpolymer (EPDM), or mixed molded materials containing any of these polyolefin materials are applied. In the case of a body, adhesion is difficult, and it has been difficult with conventional techniques to satisfy the required properties of adhesion.
JP-A-57-182350 JP 59-24771 A JP-A-61-268720 Japanese Unexamined Patent Publication No. Sho 63-112642

  The main object of the present invention is to provide an adhesive composition for difficult-to-adhere base materials that can provide sufficient adhesive strength to difficult-to-adhere base materials that are difficult to adhere by conventional adhesive techniques.

  As a result of intensive studies in view of the above circumstances, the present inventors have used a composition capable of reducing the gel fraction of a resin component containing an organic polymer having a reactive silicon group, thereby making it difficult to adhere to a substrate. The present inventors have found that the adhesion performance to can be secured and have reached the present invention.

That is, the present invention
(1) Reactivity including an organic polymer (A) having an average of 0.8 or more reactive silicon groups in one molecule, a crosslinking regulator (B), a catalyst (C) and a filler (D) A resin composition and an adhesive using the same.
(2) Preferably, a reactive resin composition having an average of 0.8 to 1.4 reactive silicon groups in component (A), and an adhesive using the same.
(3) As a preferable crosslinking regulator (B),
(Bi) a silicon compound having one silicon atom in the molecule and the total number of hydroxyl groups and hydrolyzable groups bonded to the silicon atom being one or two (here, hydrolyzable group Is a group that can react with moisture to form a silanol group with a silane atom),
(B-ii) The number of silicon atoms in the molecule is 2 to 20, the total number of hydroxyl groups and hydrolyzable groups bonded to any silicon atom in the molecule is 2 to 5, and each silicon atom In which the total number of hydroxyl groups and hydrolyzable groups bonded to the same silicon atom is 0 or 1, and (B-iii) a silicon compound R ⁴ —NH—R ¹ —Si of the following formula (1) R ² ) _z (R ³ ) _3-z (1)
(Wherein R ¹ is a branched or cyclic alkylene group, an arylene group, an alkalinene group, or an alkarylalkylene group, and when R ¹ has 4 or more carbon atoms, these groups are all One or more oxygen atoms or (poly) sulfide bonds may be included, R ² is an alkyl group having 1 to 6 carbon atoms, an aryl or alkaryl group having 5 to 20 carbon atoms. R ³ is a C1 to C6 alkoxy group or a C3 to C5 ketooximate group, R ⁴ is a hydrogen or hydrocarbon group, or an amine containing a nitrogen atom to which it is thermally attached to itself. A group that forms a group, and z is 0 or 1)
The compound chosen from is mentioned.
(Alkalylene group means a divalent hydrocarbon group in which one of the bonds is on the aryl group and the other is on the alkyl group. The alkaryl group is on the aryl group. An aryl group having an alkyl group.)
(4) The preferable compounding quantity of a filler (D) is 10-300 weight part with respect to 100 weight part of an organic polymer (A).
(5) The main chain skeleton of the organic polymer (A) is preferably an alkylene oxide polymer.
(6) The number average molecular weight of the organic polymer (A) is preferably 10,000 to 100,000.

  The composition of the present invention has a gel fraction based on the total amount of the (A) component, the (B) component, and the (C) component of a cured product obtained by curing for 8 days at room temperature and normal humidity. It is preferable to adjust so that it may become less than 20 weight%.

  The adhesive comprising the composition of the present invention has a sufficient adhesive strength for rubber-based substrates and polyolefin-based substrates, which are conventionally known as difficult-to-adhere substrates, and is a composition for adhering to difficult-to-adhere substrates. It is particularly useful as a product.

  The main chain skeleton of the organic polymer (A) having 0.8 or more reactive silicon groups in one molecule used in the present invention is not particularly limited, and those having various main chain skeletons can be used. .

  Specific examples of the main chain skeleton include polyoxyalkylene polymers, hydrocarbon polymers, polyester polymers, (meth) acrylic acid ester (co) polymers, vinyl polymers, graft polymers, polysulfides. Examples are a polymer, a polyamide polymer, and a polycarbonate polymer.

  Examples of the polyoxyalkylene polymer include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, and the like. It is done.

  Examples of the hydrocarbon polymer include ethylene-propylene copolymer, polyisobutylene, a copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or a copolymer of butadiene and acrylonitrile and / or styrene, Examples thereof include polybutadiene, isoprene or a copolymer of butadiene and acrylonitrile and styrene, and a hydrogenated polyolefin polymer obtained by hydrogenating these polyolefin polymers.

  Examples of polyester polymers include condensation polymers of dibasic acids such as adipic acid and glycols, or ring-opening polymers of lactones. Also, for example, condensation polymerization of terephthalic acid or isophthalic acid and bisphenol A. The diallyl phthalate polymer obtained in this way is mentioned.

  Examples of the (meth) acrylic acid ester-based (co) polymer include polymers obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate.

  Examples of other vinyl polymers include polymers obtained by radical polymerization of monomers such as vinyl acetate, acrylonitrile, and styrene.

  Examples of the graft polymer include a polymer obtained by reacting an organic polymer with a vinyl monomer.

  Polyamide polymers include nylon 6 obtained by ring-opening polymerization of ε-caprolactam, nylon 6 · 6 obtained by polycondensation of hexamethylenediamine and adipic acid, and polycondensation of hexamethylenediamine and sebacic acid. Nylon 6 · 10 obtained, nylon 11 obtained by condensation polymerization of ε-aminoundecanoic acid, nylon 12 obtained by ring-opening polymerization of ε-aminolaurolactam, and two or more components of the above nylon Examples thereof include copolymer nylon.

  Examples of the polycarbonate-based polymer include a polymer obtained by condensation polymerization of bisphenol A and carbonyl chloride.

  Among the polymers having the main chain skeleton, polyoxyalkylene polymers, hydrocarbon polymers, polyester polymers, (meth) acrylic acid ester (co) polymers, polycarbonate polymers are available and It is preferable because it is easy to manufacture.

  Furthermore, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester copolymers have a relatively low glass transition temperature. The resulting composition is particularly preferred because of its excellent cold resistance.

  Furthermore, the polyoxyalkylene polymer is most preferable in terms of good workability and high degree of freedom in the compounding system.

  The main chain skeleton of the organic polymer (A) may contain other components such as a urethane bond component as long as the effects of the present invention are not significantly impaired.

  The urethane-bonding component is not particularly limited, and examples thereof include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; polyhydrides such as aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate. Examples thereof include those obtained from a reaction between an isocyanate compound and the above-mentioned polyols having various main chain skeletons.

The reactive silicon group contained in the component (A) is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of forming a siloxane bond by a reaction accelerated by a silanol condensation catalyst. As the reactive silicon group, the general formula (2):
-(SiR ⁵ _2-b X _b O) _m -SiR ⁶ _3-a X _a (2)
Wherein R ⁵ and R ⁶ are the same or different alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO—. A triorganosiloxy group, when two or more R ⁵ or R ⁶ are present, they may be the same or different, where R ′ is a monovalent carbon of 1 to 20 carbon atoms; Three R's may be the same or different, and X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they may be the same good, good .a is 0, 1, 2 or 3 be different, b is 0, 1 or for b in 2 respectively. the m-number of _{^{(SiR 5 2-b X b}} O) group, They may be the same or different, m is It represents an integer of 19. However, a group represented by shall satisfy a + Σb ≧ 1) and the like.

  It does not specifically limit as a hydrolysable group, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable. Particularly preferred.

  Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and (a + Σb) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different.

In particular, the general formula (3):
-SiR ⁶ _3-a X _a (3)
A reactive silicon group represented by the formula (wherein R ⁶ and X are the same as described above; a is an integer of 1 to 3) is preferable because it is easily available.

Specific examples of R ⁵ and R ⁶ in the general formulas (2) and (3) include, for example, an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, benzyl Aralkyl groups such as groups,
Examples thereof include a triorganosiloxy group represented by (R ′) ₃ SiO— in which R ′ is a methyl group, a phenyl group or the like. Of these, a methyl group is particularly preferred.

  More specific examples of the reactive silicon group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a methyldimethoxysilyl group, a methyldiethoxysilyl group, and a methyldiisopropoxysilyl group.

  The introduction of the reactive silicon group into the component (A) may be performed by a known method. For example, the following methods are mentioned.

  (B) An organic polymer having an unsaturated group is reacted with an organic polymer having a functional group such as a hydroxyl group in the molecule by reacting an organic compound having an active group and an unsaturated group reactive to the functional group. Get coalesced. Or, for example, when an epoxide is ring-opening polymerized to obtain an organic polymer, an unsaturated group-containing epoxide is ring-opening copolymerized to obtain an unsaturated group-containing organic polymer. By copolymerizing, an unsaturated group-containing organic polymer is obtained. Next, hydrosilane having a reactive silicon group is allowed to act on the obtained reaction product to effect hydrosilylation.

  (B) An organic polymer containing an unsaturated group obtained in the same manner as in the method (a) is reacted with a compound having a mercapto group and a reactive silicon group.

  (C) An organic polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in the molecule is reacted with a compound having a reactive functional group and a reactive silicon group.

  Among the above methods, the method (a) or the method (c) of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group is high in a relatively short reaction time. It is preferable because a conversion rate can be obtained. Furthermore, the organic polymer having a reactive silicon group obtained by the method (a) is a composition having a lower viscosity and better workability than the polymer obtained by the method (c). Since the polymer obtained by the method (b) has a strong odor based on mercaptosilane, the method (a) is particularly preferred.

  Specific examples of the hydrosilane compound used in the method (a) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, and methyldiethoxysilane. Alkoxysilanes such as methyldimethoxysilane and phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; bis (dimethylketoxymate) methylsilane, bis (cyclohexylketoximate) methylsilane Examples thereof include, but are not limited to, ketoximate silanes. Among these, halogenated silanes and alkoxysilanes are particularly preferable, and alkoxysilanes are particularly preferable because the hydrolyzability of the resulting composition is gentle and easy to handle.

  As a synthesis method of (b), for example, a compound having a mercapto group and a reactive silicon group is introduced into an unsaturated bond site of an organic polymer by radical addition reaction in the presence of a radical initiator and / or a radical generating source. Examples of the method include, but are not limited to. Specific examples of the compound having a mercapto group and a reactive silicon group include, for example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxy. Although silane etc. are mention | raise | lifted, it is not limited to these.

  As a 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 (c), for example, the method described in JP-A-3-47825 can be mentioned. However, it is not particularly limited. Specific examples of the compound having an isocyanate group and a reactive silicon group include, for example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-isocyanatepropylmethyldiethoxy. Although silane etc. are mention | raise | lifted, it is not limited to these.

  The component (A) may be linear or branched, and its number average molecular weight is preferably about 10,000 to 100,000, more preferably 15,000 to 50,000 in terms of polystyrene in GPC. is there. If the number average molecular weight is less than 10,000, the composition has a high hardness, which is disadvantageous. If the number average molecular weight exceeds 100,000, the composition tends to be disadvantageous in terms of workability because of high viscosity.

  The reactive silicon group may be at the end or inside of the organic polymer molecular chain, or at both the end and inside. In particular, when a reactive silicon group is present only at the molecular end, a network of polymer components contained in the composition is efficiently constructed, so that an effective amount of network can be obtained with a small amount of reactive silicon group. It is preferable because it is possible.

Various methods are conceivable as a method for measuring the introduction rate of the reactive silicon group, but at present it can be calculated from the integrated value of the terminal into which the reactive silicon group has been introduced by ¹ H-NMR spectrum.

  In order to measure the amount of mesh formation, there is a method of measuring the gel fraction. As a method for measuring the gel fraction, a method is generally used in which a cured product wrapped with a wire mesh or the like is placed in a solvent in which a polymer is dissolved, and the amount of gel remaining without being extracted is measured.

The polyoxyalkylene polymer essentially has the general formula (4):
-R ⁷ -O- (4)
(Wherein R ⁷ is a linear or branched alkylene group having 1 to 14 carbon atoms), and R ⁷ in the general formula (4) is a branched alkylene group. The number of carbon atoms is more preferably 2-4. Specific examples of the repeating unit represented by the general formula (4) include
_{-CH 2 O -, - CH 2} CH 2 O -, - CH 2 CH (CH 3) O-
_{-CH 2 CH (C 2 H 5} ) O -, - CH 2 C (CH 3) 2 -O-
_{-CH 2 CH 2 CH 2 CH 2} O-
Etc.

  The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, a polymer composed mainly of a propylene oxide polymer is preferred because it is amorphous and has a relatively low viscosity.

  Examples of the method for synthesizing the polyoxyalkylene polymer include a polymerization method using an alkali catalyst such as KOH, and a complex obtained by reacting an organoaluminum compound and porphyrin as disclosed in JP-A-61-215623. Polymerization method using transition metal compound-porphyrin complex catalyst, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Patent 3,278,457, US Patent 3,278,458, US Patent 3,278,459, US Patent 3,427,256, US Patent 3,427,334, Polymerization method using double metal cyanide complex catalyst as shown in U.S. Pat. No. 3,427,335, polymerization method using catalyst comprising polyphosphazene salt exemplified in JP-A-10-273512, phosphazene exemplified in JP-A-11-060722 Using a compound catalyst Polymerization method, and the like, but not particularly limited.

  A method for producing a polyoxyalkylene polymer having a reactive silicon group is disclosed in JP-B Nos. 45-36319, 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767. JP-A-55-13468, 57-164123, JP-B-3-2450, US Pat. No. 3,632,557, US Pat. No. 4,345,053, US Pat. No. 4,366,307, US Pat. No. 4,960,844, etc. -197631, 61-215622, 61-215623, 61-218632, JP-A-3-72527, JP-A-3-47825, and JP-A-8-231707. Polyoxya with a narrow molecular weight distribution with a high molecular weight with a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less Killen polymer can be exemplified, but not particularly limited thereto.

  The above polyoxyalkylene polymers having a reactive silicon group may be used alone or in combination of two or more.

  The saturated hydrocarbon polymer is a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and the polymer constituting the skeleton is (1) ethylene, propylene, 1-butene, isobutylene, or the like. After polymerizing such an olefinic compound having 1 to 6 carbon atoms as a main monomer, or (2) homopolymerizing a diene compound such as butadiene or isoprene, or copolymerizing with the olefinic compound However, isobutylene-based polymers and hydrogenated polybutadiene-based polymers can be easily introduced with functional groups at the terminals, the molecular weight can be easily controlled, and the number of terminal functional groups can be adjusted. An isobutylene polymer is particularly preferable because of its ease of synthesis.

  Those whose main chain skeleton is a saturated hydrocarbon polymer have characteristics of excellent heat resistance, weather resistance, durability, and moisture barrier properties.

  In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, or may be a copolymer with other monomers, but the repeating unit derived from isobutylene is 50 from the viewpoint of rubber properties. What contains more than weight% is preferable, What contains 80 weight% or more is more preferable, What contains 90 to 99 weight% is especially preferable.

  As a method for synthesizing a saturated hydrocarbon polymer, various polymerization methods have been reported so far, but in particular, many so-called living polymerizations have been developed in recent years. In the case of saturated hydrocarbon polymers, particularly isobutylene polymers, the inifer polymerization found by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, 15, 2843). It is known that a molecular weight of about 500 to 100,000 can be polymerized with a molecular weight distribution of 1.5 or less, and various functional groups can be introduced at the molecular ends.

  Examples of the method for producing a saturated hydrocarbon polymer having a reactive silicon group include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, Although described in Japanese Laid-Open Patent Publication No. 1-197509, Japanese Patent Publication No. 2539445, Japanese Patent Publication No. 2873395, and Japanese Patent Application Laid-Open No. 7-53882, it is not particularly limited thereto.

  The saturated hydrocarbon polymer having a reactive silicon group may be used alone or in combination of two or more.

  In the present invention, as the organic polymer of component (A), one having a molecular chain that is a (meth) acrylic acid ester copolymer can be used.

  It does not specifically limit as a (meth) acrylic-ester type monomer which comprises the principal chain of the said (meth) acrylic-ester type polymer, A various thing can be used. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 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, (meth) acrylic Acid toluyl, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ -(Methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic acid 2- Perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutyl ethyl, (meth) acrylic acid 2-perfluoroethyl, (meth) acrylic acid perfluoromethyl, (meth) acrylic acid diper Fluoromethylmethyl, (meth) acrylic acid 2-perf (Meth) such as fluoromethyl-2-perfluoroethylmethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate Examples include acrylic acid monomers. In the (meth) acrylic acid ester copolymer, the following vinyl monomers can be copolymerized together with the (meth) acrylic acid ester monomer. Examples of the vinyl monomer include styrene monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid, and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, Methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohex Maleimide monomers such as lumaleimide; Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, cinnamon Examples thereof include vinyl esters such as vinyl acid; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These may be used alone or a plurality of these may be copolymerized. Especially, the polymer which consists of a styrene-type monomer and a (meth) acrylic-acid type monomer from the physical property of a product etc. is preferable. More preferably, it is a (meth) acrylic polymer composed of an acrylate monomer and a methacrylic acid ester monomer, particularly preferably an acrylic polymer composed of an acrylate monomer, and further preferably composed of butyl acrylate. It is a polymer. In the present invention, these preferable monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, it is preferable that these preferable monomers are contained in a weight ratio of 40%. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  The method for synthesizing the (meth) acrylic acid ester copolymer is not particularly limited, and may be performed by a known method. However, a polymer obtained by a normal free radical polymerization method using an azo compound or a peroxide as a polymerization initiator has a problem that the molecular weight distribution is generally as large as 2 or more and the viscosity is increased. Yes. Therefore, in order to obtain a (meth) acrylate copolymer having a narrow molecular weight distribution and low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio For this, it is preferable to use a living radical polymerization method.

  Among the living radical polymerization methods, an atom transfer radical polymerization method in which a (meth) acrylate monomer is polymerized using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is preferable. In addition to the characteristics of the above-mentioned living radical polymerization method, this method is a method by which a polymer having a halogen or the like that is relatively advantageous for functional group conversion reaction can be obtained, and the design of initiators and catalysts is free. Since the degree is high, it is suitable as a method for producing a (meth) acrylic acid ester-based copolymer having a reactive silicon group. Examples of this atom transfer radical polymerization method include the method shown in Matyjaszewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614.

  As a method for producing a (meth) acrylic acid ester-based copolymer having a reactive silicon group, for example, Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, Japanese Patent Application Laid-Open No. Hei 6-221922, etc. A production method using a free radical polymerization method using a transfer agent is disclosed. Japanese Patent Application Laid-Open No. 9-272714 discloses a production method using an atom transfer radical polymerization method, but is not particularly limited thereto.

  The reactive silicon group of the component (A) may be at the end or inside of the organic polymer molecular chain, or may be at both the end and inside. In particular, when the reactive silicon group is only at the end of the polymer main chain, the effective network chain amount of the polymer component finally formed in the composition increases, so a small amount of reactive silicon group. Is preferable from the standpoint that it is easy to obtain an effective amount of mesh.

  As the polymerization method of the component (A), the living radical polymerization method is more preferable because it has a low viscosity due to the narrow molecular weight distribution and can introduce a crosslinkable functional group at the molecular chain terminal at a high rate. Atom transfer radical polymerization is particularly preferred.

  The (meth) acrylic acid ester-based copolymer having a reactive silicon group may be used alone or in combination of two or more.

  A method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a reactive silicon group and a (meth) acrylic acid ester copolymer having a reactive silicon group is disclosed in JP-A-59-122541, Although proposed in Japanese Patent Laid-Open Nos. 63-112642, 6-172631, and 11-116763, the invention is not particularly limited thereto.

A preferred specific example of the (meth) acrylic acid ester copolymer of component (A) has a reactive silicon group and a molecular chain substantially having the following general formula (5):
—CH ₂ —C (R ⁸ ) (COOR ⁹ ) — (5)
(Wherein R ⁸ is a hydrogen atom or a methyl group, R ⁹ is an alkyl group having 1 to 9 carbon atoms) (meth) acrylic acid ester monomer having an alkyl group having 1 to 9 carbon atoms Unit and the following general formula (6):
—CH ₂ —C (R ⁸ ) (COOR ¹⁰ ) — (6)
(Wherein R ⁸ is the same as described above, and R ¹⁰ represents an alkyl group having 10 or more carbon atoms) and is a copolymer comprising a (meth) acrylic acid ester monomer unit having an alkyl group having 10 or more carbon atoms. In this method, a polymer is blended with a polyoxyalkylene polymer having a reactive silicon group.

As R ^{9 in the} general formula (5), for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a 2-ethylhexyl group, etc., 1 to 9, preferably 1 to 4, More preferably, 1-2 alkyl groups are mentioned. The alkyl group of R ⁹ may alone, or may be a mixture of two or more.

The ^{R 10} in the general formula (6), such as lauryl group, tridecyl group, cetyl group, stearyl group, carbon atoms, such as behenyl group 10 or more, usually 10 to 30, preferably of the long-chain from 10 to 20 alkyl Group. Incidentally, as with the alkyl groups of R ¹⁰ is the R ^9, alone may or may be a mixture of two or more.

  The molecular chain of the (meth) acrylic acid ester-based copolymer is substantially composed of monomer units of the formulas (5) and (6), and the term “substantially” here refers to the copolymer. It means that the total of the monomer units of the formula (5) and the formula (6) present therein exceeds 50% by weight. The sum of the monomer units of formula (5) and formula (6) is preferably 70% by weight or more.

  Further, the abundance ratio of the monomer unit of the formula (5) and the monomer unit of the formula (6) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40 by weight.

  Examples of monomer units other than those represented by formula (5) and formula (6) that may be contained in the copolymer include acrylic acid such as acrylic acid and methacrylic acid; acrylamide, methacrylamide, N-methylolacrylamide, Monomers containing an amide group such as N-methylol methacrylamide, an epoxy group such as glycidyl acrylate and glycidyl methacrylate, and an amino group such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and aminoethyl vinyl ether; other acrylonitrile, styrene, α-methylstyrene Monomer units derived from alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

  The organic polymer (A) having a reactive silicon group may be used alone or in combination of two or more.

  Specifically, it comprises a polyoxyalkylene polymer having a reactive silicon group, a saturated hydrocarbon polymer having a reactive silicon group, and a (meth) acrylic acid ester copolymer having a reactive silicon group. An organic polymer obtained by blending two or more selected from the group can also be used.

  Organic polymers obtained by blending a saturated hydrocarbon polymer having a reactive silicon group and a (meth) acrylic acid ester copolymer having a reactive silicon group are disclosed in JP-A-1-168774 and JP-A-2000-. Although it is proposed in Japanese Patent No. 186176, etc., it is not particularly limited thereto.

  Furthermore, as a method for producing an organic polymer obtained by blending a (meth) acrylic acid ester-based copolymer having a reactive silicon functional group, in the presence of an organic polymer having a reactive silicon group, A method of polymerizing a (meth) acrylic acid ester monomer can be used. This production method is specifically disclosed in JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, etc. It is not limited to these.

  Various compounds are used for the crosslinking regulator of the component (B) in the present invention. As the component (B) in the present invention, a compound that causes low modulus of rubber properties after the reaction is used.

  Examples of component (B) include (Bi) intramolecular such as diphenylsilanediol, diphenyldimethoxysilane, dimethyldimethoxysilane, trimethylsilanol, triethylsilanol, triphenylsilanol, diphenylmethylsilanol, phenyldimethylsilanol. A silicon compound having one silicon atom and the total number of hydroxyl groups and hydrolyzable groups bonded to the silicon atom being one or two (wherein the hydrolyzable group reacts with moisture) (B-ii) in the molecule such as 1,3,5-triphenyl-1,3,5-trimethoxy-1,5-dimethylsiloxane and the like. The number of silicon atoms is 2 to 20, and the hydroxyl group and water bonded to any silicon atom in the molecule. The total number is 2 to 5 resolvable base, silicon compounds the total number of hydroxyl and a hydrolyzable group bonded to the same silicon atom at each silicon atom is 0 or 1.

  In the silicon compound of (Bi) or (B-ii), examples of the group other than the hydroxyl group and hydrolyzable group bonded to the silicon atom include an alkyl group having 1 to 20 carbon atoms and an aryl group having 5 to 20 carbon atoms. And an aralkyl group having 6 to 20 carbon atoms.

Further, a silicon compound (B-iii) represented by the formula (1) is also preferable as a crosslinking regulator.
_{^{R 4 -NH-R 1 -Si (}} R 2) z (R 3) 3-z (1)
(Wherein R ¹ is a branched or cyclic alkylene group, an arylene group, an alkalinene group, or an alkarylalkylene group, and when R ¹ has 4 or more carbon atoms, these groups are all One or more oxygen atoms or (poly) sulfide bonds may be included, R ² is an alkyl group having 1 to 6 carbon atoms, an aryl or alkaryl group having 5 to 20 carbon atoms. R ³ is a C1 to C6 alkoxy group or a C3 to C5 ketooximate group, R ⁴ is a hydrogen or hydrocarbon group, or an amine containing a nitrogen atom to which it is thermally attached to itself. A group that forms a group, and z is 0 or 1)
The alkali-lene group means a divalent hydrocarbon group in which one of the bonds is on the aryl group and the other is on the alkyl group. An alkaryl group is an aryl group having an alkyl group in which a bond is present on the aryl group. The alkaryl alkylene group is a divalent group in which an alkylene group is further bonded to the aryl group of the alkaryl group, and the two bonds exist on different alkyl groups.

Specific examples of R ¹ include 1,3-butylene, 1,2-butylene or 2,2-dimethyl-1,3-propylene, 3-methylbutylene, 3,3-dimethylbutylene, 2-ethylhexylene, 1,4-diethylenephenylene, 3-phenyl-1,3-propylene, 1,4-cyclohexylene, 1,4-diethylenecyclohexylene, and the like.

Preferred R ¹ groups are branched alkylene groups having 4 to 8 carbon atoms.

Specific examples of R ² are methyl, ethyl, propyl, isopropyl, butyl, hexyl, phenyl, cyclohexyl, tolyl and the like.

Preferred R ² groups are absent (z = 0) or are methyl groups.

Specific examples of R ³ include methoxy, ethoxy, isopropoxy, n- propoxy, phenoxy, 2-phenylethoxy, dimethyl ketoximo, methylethyl ketoximo include diethyl ketoximo like.

Preferred R ³ groups are methoxy and ethoxy.

Specific examples of R ⁴ include hydrogen, methyl, ethyl, 2-aminoethyl, propyl, 3-aminopropyl, butyl, cyclohexyl, phenyl, methylphenyl, 2-cyanoethyl, isopropoxyethyl and the like. When R ⁴ is a substituted hydrocarbon, acceptable substituents include cyano, alkoxy and amino. Further, when exposed to a temperature of about 150 ° C. or higher during the reaction, R ⁴ may be a group that thermally deblocks to form an amine.

  Preferred compounds as the compound of formula (1) are N-ethyl-3-aminoisobutyltrimethoxysilane, N-ethyl-3-aminoisobutyldimethoxymethylsilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, 4 -Amino-3,3-dimethylbutyldimethoxymethylsilane, N-methyl-4-amino-3,3-dimethylbutyltrimethoxysilane, aminoisopropoxyethyltrimethoxysilane, aminoisopropoxypropyltrimethoxysilane and the above methoxy group It is substituted with an ethoxy group or a mixture of an ethoxy group and a methoxy group.

  The catalyst (C) in the present invention may be any catalyst for reaction of the reactive group of the organic polymer (A) having 0.8 or more reactive silicon groups on average in one molecule.

  Specific examples thereof include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetraacetylacetonate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctate, dibutyltin diethylhexanolate, dibutyltin dimethyl maleate, dibutyltin Diethyl maleate, dibutyltin dibutyl maleate, dibutyltin dioctyl maleate, dibutyltin ditridecyl maleate, dibutyltin dibenzyl maleate, dibutyltin diacetate, dioctyltin diethyl maleate, dioctyltin dioctyl maleate, dibutyltin dimethoxide, dibutyltin dinonyl Phenoxide, dibutenyl tin oxide, dibutyltin diacetyl Tetravalent tin compounds such as a settonate, dibutyltin diethylacetoacetonate, a reaction product of dibutyltin oxide and a phthalate; divalent tin compounds such as tin octylate, tin naphthenate, tin stearate, tin versatate; Organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium compounds such as zirconium tetraacetylacetonate; lead octylate; butylamine, octylamine, dibutylamine, mono Ethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, laurylamine, cyclohexyl Min, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole 1,8-diazabicyclo (5,4,0) undecene-7 (DBU), amine compounds such as N, N-diethylpropanediamine, or salts of these amine compounds with carboxylic acids, etc .; excess polyamine Low molecular weight polyamide resin obtained from polybasic acid; reaction product of excess polyamine and epoxy compound; γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, etc. Silanes having amino groups Examples include silanol condensation catalysts such as pulling agents; and other known silanol condensation catalysts such as other acidic catalysts and basic catalysts. These catalysts may be used alone or in combination of two or more.

  The amount of catalyst used is preferably about 0.01 to 20 parts by weight, more preferably about 0.1 to 10 parts by weight, per 100 parts by weight of component (A).

  If the amount of the catalyst used is too small, the reaction rate becomes slow and it is difficult to proceed sufficiently. On the other hand, if the amount of the catalyst used is too large, local heat generation and foaming occur during the reaction, making it difficult to obtain a good composition, which is not preferable.

  The (D) filler in the present invention is not limited to a specific filler. Specific examples thereof include fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black, calcium carbonate, magnesium carbonate, calcium oxide, calcium hydroxide, diatomaceous earth, calcined clay, clay, talc and the like. Organic fillers such as system fillers, PVC powders, acrylic resin powders, polyolefin powders; fibrous fillers such as asbestos, glass fibers and filaments; inorganic balloons such as shirasu balloons, glass balloons, saran balloons, phenol balloons, etc. Organic balloons are exemplified, and one or more of these may be used. The filler is preferably used in an amount of 10 to 300 parts by weight, particularly 50 to 200 parts by weight, based on 100 parts by weight of component (A). When the amount is less than 10 parts by weight, the effect as a filler is hardly exhibited, and when the amount exceeds 300 parts by weight, the mixing property and workability tend to be inconvenient.

  The composition of the present invention is blended with a crosslinking regulator (B) in order to adjust the gel fraction of the cured product. The gel fraction may be adjusted by increasing or decreasing the blending amount of the crosslinking regulator (B) or changing the type and amount of the catalyst (C). As a standard for adjustment, the gel fraction based on the total amount of the components (A), (B) and (C) of the cured product obtained by curing for 8 days at room temperature and normal humidity is 20% by weight. It is preferable to adjust so that it may become less. Preferably it is less than 10%.

  If necessary, a tackifier resin, a plasticizer, an adhesion promoter, a solvent, other additives, and the like can be added to the composition of the present invention.

  Specific examples of tackifying resins that can be used in the composition of the present invention include styrene (co) polymers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof, and coumarone-indene. Resin, coumarone resin mixed with naphthene resin, phenol resin, rosin, coumarone resin, pt-butylphenol-acetylene resin, phenol formaldehyde resin with low degree of polymerization and low softening point (about 60-100 ° C), xylene -Phenolic resins, xylene resins, terpenes that improve adhesion and heat resistance as well as tackiness-phenolic resins, terpene resins such as terpene resins, synthetic polyterpene resins, aromatic hydrocarbon resins, aliphatic resins Hydrocarbon resin, aliphatic cyclic hydrocarbon resin, hydrogenated hydrocarbon Petroleum hydrocarbon resins such as fat, rosin and rosin pentaerythritol ester, rosin glycerol ester, hydrogenated rosin, highly hydrogenated wood resin, hydrogenated rosin methyl ester, hydrogenated rosin triethylene glycol ester Rosin derivatives such as hydrogenated rosin pentaerythritol ester, polymerized rosin, polymerized rosin glycerol ester, resin acid zinc, hardened rosin and low molecular weight polystyrene. Other special preparations are listed. These tackifying resins can be used alone or in combination of two or more. As for the usage-amount of tackifying resin, 1-150 weight part is preferable with respect to 100 weight part of (A) component.

  Specific examples of the plasticizer used in the composition of the present invention include phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, and butyl phthalyl butyl glycolate; Non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate; phosphate esters such as tricresyl phosphate and tributyl phosphate; hydrocarbon plasticizers such as polybutene, polybutadiene and non-reactive polyisobutylene; Examples include alkylsulfonic acid phenyl esters such as Mesamol II (manufactured by Bayer); epoxy plasticizers such as epoxidized soybean oil and epoxidized linseed oil, and alkylarylsulfonamides.

  Moreover, a polymeric plasticizer can also be used. When a high-molecular plasticizer is used, the initial physical properties can be maintained over a long period of time compared to the case where a low-molecular plasticizer that is a plasticizer that does not contain a polymer component in the molecule is used. 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 plasticizer 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; Are 1000 or more polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., or the hydroxyl groups of these polyether polyols are ester groups, ethers Polyethers such as derivatives converted into groups, etc .; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like, but are not limited thereto is not.

  These plasticizers may be used alone or in combination of two or more.

  The amount of the plasticizer used is preferably 10 to 300 parts by weight per 100 parts by weight of component (A).

  Specific examples of the adhesion-imparting agent include silane coupling agents, reactants of silane coupling agents, or compounds other than silane coupling agents. Specific examples of the silane coupling agent include isocyanate group-containing silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropylmethyldimethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldie Amino groups such as toxisilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane -Containing silanes; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane and other mercapto group-containing silanes; γ-glycidoxypropyl Trimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) Sil) Epoxy group-containing silanes such as ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N- (carboxymethyl) -β-aminoethyl-γ- Carboxysilanes such as aminopropyltrimethoxysilane; Vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-acryloyloxypropylmethyltriethoxysilane; Halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate, and the like. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives of these, can also be used as silane coupling agents. . The silane coupling agent used for this invention is normally used in 0.1-20 weight part with respect to 100 weight part of (A) component. In particular, it is preferably used in the range of 0.5 to 10 parts by weight.

  The effects of the silane coupling agent added to the composition of the present invention include various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, mortar, vinyl chloride, acrylic, polyester, polycarbonate, etc. When used as an organic substrate, it exhibits a remarkable effect of improving adhesion under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable. Specific examples other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resins, phenol resins, sulfur, alkyl titanates, and aromatic polyisocyanates. The adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesiveness-imparting agents, the adhesion to the adherend can be improved.

  Examples of the solvent include non-reactive solvents such as hydrocarbons, acetate esters, alcohols, ethers, and ketones, and there is no particular limitation as long as it is such a solvent.

  Examples of other additives include a sagging inhibitor, a colorant, an antioxidant, a light stabilizer, and an ultraviolet absorber.

  Specific examples of the sagging inhibitor include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents (thixotropic agents) may be used alone or in combination of two or more. The thixotropic agent is used in the range of 0.1 to 20 parts by weight per 100 parts by weight of component (A).

Examples of the antioxidant (anti-aging agent) include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Also described in JP-A-4-283259 and JP-A-9-194731. Similarly, Tinuvin 622LD, Tinuvin 144;
CHIMASSORB 944LD, CHIMASSORB 119FL (all manufactured by Ciba Specialty Chemicals); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68 (all of which are Asahi Denka Kogyo Co., Ltd.) Made);
Use the hindered amine light stabilizer shown in Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-114, Sanol LS-744 (all of which are manufactured by Sankyo Co., Ltd.) You can also. The amount of the antioxidant used is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, relative to 100 parts by weight of component (A).

  Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred. The light stabilizer is used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of component (A). Specific examples of the light stabilizer are also described in JP-A-9-194731.

  Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferable. The ultraviolet absorber is used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight per 100 parts by weight of component (A). It is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in combination.

  Various additives may be added to the composition of the present invention as needed for the purpose of adjusting the physical properties of the composition. Examples of such additives include, for example, adhesion improvers, storage stability improvers, flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorous peroxides. Examples include a substance decomposer, a lubricant, a pigment, a foaming agent, a solvent, and an antifungal agent. These various additives may be used alone or in combination of two or more. Specific examples other than the specific examples of the additives listed in the present specification include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-62-2904, It is described in Japanese Laid-Open Patent Publication No. 2001-72854.

  In order to impart high elongation performance, an α, β-diol or a compound having an α, γ-diol structure as disclosed in JP-A-11-080533 can also be added.

  The method for producing the composition of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, roll, kneader or the like, and each component is dissolved and mixed using a solvent. A method may be employed. The composition can be either a one-component or two-component composition.

  When the composition is of a one-component type, since all the ingredients are pre-blended, it is preferable that the water-containing ingredients are dehydrated and dried before use, or dehydrated under reduced pressure during compounding and kneading. . When the composition is of a two-component type, it is not necessary to blend a catalyst with the main ingredient containing the organic polymer, so there is little concern about gelation even if some moisture is contained in the compounding agent. When the storage stability is required, it is preferably dehydrated and dried. As the dehydration and drying method, a heat drying method is preferable in the case of a solid substance such as a powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel or the like is preferable in the case of a liquid material. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ -Storage stability is further improved by adding an alkoxysilane compound such as glycidoxypropyltrimethoxysilane.

  The amount of silicon compound capable of reacting with water such as dehydrating agent, especially vinyltrimethoxysilane, is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight per 100 parts by weight of component (A). A range is preferred.

  The composition of this invention is demonstrated based on an Example. EXAMPLES Hereinafter, the present invention will be specifically described with reference to synthesis examples and examples, but the present invention is not limited to these synthesis examples and examples.

(Synthesis Example 1)
Polyoxypropylene diol having a number average molecular weight of 25400 (polystyrene conversion value determined from GPC) is obtained by polymerizing propylene oxide using a polyoxypropylene diol having a number average molecular weight of 2000 as an initiator and a composite metal cyanide complex catalyst. Obtained. After adding 2.5 parts by weight of a 30% methanol solution of sodium methylate, devolatilization was performed at 130 ° C. until no methanol was recovered. Next, 1.3 parts by weight of allyl chloride was added and reacted for 5 hours, after which unreacted allyl chloride was removed by devolatilization under reduced pressure, then purified with hexane and water, and an average of two allyl end groups in one molecule. An oxypropylene polymer (P1) containing was obtained.

(Synthesis Example 2)
By polymerizing propylene oxide using a double metal cyanide complex catalyst with a polyoxypropylenediol having a number average molecular weight of 2000 as an initiator, a number average molecular weight of 38000 (polystyrene conversion value determined by GPC), a molecular weight distribution of 1.4 Of polyoxypropylene diol was obtained. After adding 2 parts by weight of a 30% methanol solution of sodium methylate, devolatilization was performed at 130 ° C. until no methanol was recovered. Next, 1.2 parts by weight of allyl chloride was added and reacted for 5 hours. Unreacted allyl chloride was removed by devolatilization under reduced pressure, then purified with hexane and water, and an average of two allyl end groups in one molecule. An oxypropylene polymer (P2) containing was obtained.

(Synthesis Example 3)
Polymerization of propylene oxide using a polyoxypropylene diol having a number average molecular weight of 2000 as an initiator and a double metal cyanide complex catalyst, a number average molecular weight of 15,000 (polystyrene conversion value determined by GPC), a molecular weight distribution of 1.1 Of polyoxypropylene diol was obtained. After adding 4.2 parts by weight of a 30% methanol solution of sodium methylate, devolatilization was performed at 130 ° C. until no methanol was recovered. Then, after adding 2.8 parts by weight of allyl chloride and reacting for 5 hours, unreacted allyl chloride was removed by devolatilization under reduced pressure, and then purified with hexane and water, and an average of two allyl end groups in one molecule. An oxypropylene polymer (P3) containing was obtained.

(Synthesis Example 4)
0.4 mol of dimethoxymethylsilane is reacted in the presence of chloroplatinic acid with respect to 1 mol of allyl group of P1 obtained in Synthesis Example 1, and an oxypropylene polymer (P4) having a dimethoxymethylsilyl group at the molecular end is obtained. Obtained.

(Synthesis Example 5)
By reacting 0.6 mole of dimethoxymethylsilane with 1 mole of P1 allyl group obtained in Synthesis Example 1 in the presence of chloroplatinic acid, an oxypropylene polymer (P5) having a dimethoxymethylsilyl group at the molecular end is obtained. Obtained.

(Synthesis Example 6)
0.3 mol of dimethoxymethylsilane was reacted in the presence of chloroplatinic acid with respect to 1 mol of allyl group of P1 obtained in Synthesis Example 1 to obtain an oxypropylene polymer (P6) having a dimethoxymethylsilyl group at the molecular end. Obtained.

(Synthesis Example 7)
By reacting 0.65 mol of dimethoxymethylsilane with 1 mol of P2 allyl group obtained in Synthesis Example 2 in the presence of chloroplatinic acid, an oxypropylene polymer (P7) having a dimethoxymethylsilyl group at the molecular end is obtained. Obtained.

(Synthesis Example 8)
0.4 mol of dimethoxymethylsilane is reacted in the presence of chloroplatinic acid with respect to 1 mol of allyl group of P3 obtained in Synthesis Example 3, and an oxypropylene polymer (P8) having a dimethoxymethylsilyl group at the molecular end is obtained. Obtained.

(Synthesis Example 9)
Using a polyoxypropylene diol having a number average molecular weight of 2000 as an initiator and a composite metal cyanide complex catalyst, by polymerizing propylene oxide, a polyoxypropylene diol having a number average molecular weight of 25400 (polystyrene conversion value determined by GPC) is obtained. Obtained. 0.4 mol of γ-isocyanatopropyltrimethoxysilane is added to 1 mol of hydroxyl group of the obtained polypropylene glycol to carry out a urethanation reaction to obtain an oxypropylene polymer (P9) having a trimethoxysilyl group at the molecular end. It was.

  A summary of the polymers obtained in Synthesis Examples 4 to 9 is shown in Table 1. Table 2 shows the measurement results of the gel fraction.

[Method for Measuring Silylation Rate (Method for Measuring Silylation Rate (%) Obtained from ¹ H-NMR)]
-The peak integral value of the polymer main chain is used as an internal standard and is calculated from the integral decrease value of the allyl group peak before and after the silylation reaction.

[Measurement method of gel fraction]
・ Polymer, crosslinking modifier, catalyst and water are mixed in the specified amount shown in the table, defoamed with a centrifuge (3000rpm, 1min), and then poured into a mold (width 14cm x height 7cm x height 3mm). . After curing at 23 ° C. for 8 days, about 100 mg is cut from the cured sheet and placed in a wire mesh. After dipping in acetone at 23 ° C. for 1 day, pulling it up, and lightly washing with acetone, it is dried in an oven at 50 ° C. for about 2 hours. The gel fraction is calculated from the change in weight before and after immersion.

(Example 1)
100 parts by weight of P4 obtained in Synthesis Example 4 as an organic polymer (A) component having an average of 0.8 or more reactive silicon groups in one molecule, and diphenyldimethoxysilane as a crosslinking regulator (B) 1 part by weight (hereinafter referred to as B-1), 1 part by weight of U-220 (dibutyltin diacetylacetonate) as the catalyst of component (C), and Ultraflex (collagen calcium carbonate, Specialty Minerals, Inc.) as filler (D) 120 parts by weight, and further 2 parts by weight of vinyltrimethoxysilane (A-171, manufactured by Nihon Unicar Co., Ltd.) were sufficiently kneaded to prepare a one-part composition, filled into a cartridge, and subjected to the following test. did.

(Adhesion test method)
A T-type peel test piece having an adhesive layer thickness of 1 mm was prepared. After curing at 23 ° C. for 7 days, a T-type peel test was performed at a test speed of 50 mm / min.

(Difficult adhesive substrate)
SBR (styrene-butadiene rubber) substrate;
Engineering Test Service Co., Ltd., 25 × 100 × 3mm
EPDM substrate;
Engineering Test Service Co., Ltd., 25 × 100 × 3mm
TPO substrate;
Waterprof membrane sample manufactured by Carlisle (base material based on thermoplastic polyolefin and polypropylene resin)
25 × 100 × 1.5mm
(Example 2)
A composition was prepared in the same manner as in Example 1 except that N-ethyl-3-aminoisobutyltrimethoxysilane (hereinafter referred to as B-2) was used as the crosslinking regulator (B), and the same evaluation was performed. It was.

(Example 3)
A composition was prepared in the same manner as in Example 1 except that 100 parts by weight of P5 obtained in Synthesis Example 5 was used as the component (A) and 4 parts by weight of B-1 was used. Went.

Example 4
A composition was prepared in the same manner as in Example 1 except that 100 parts by weight of P7 obtained in Synthesis Example 7 was used as the component (A) and 5 parts by weight of B-2 was used. Went.

(Example 5)
As in Example 1, except that 100 parts by weight of P8 obtained in Synthesis Example 8 is used as the component (A), 1.5 parts by weight of B-1 is used, and 150 parts by weight of the component (D) is used. A composition was prepared by the method described above, and the same evaluation was performed.

(Example 6)
As component (A), P9 obtained in Synthesis Example 9 and P4 obtained in Synthesis Example 4 were mixed at a 1: 1 weight ratio to use 100 parts by weight in total, and 3 parts by weight of B-1 was used. (C) A composition was prepared in the same manner as in Example 1 except that 0.1 part by weight of dibutyltin dilaurate (hereinafter referred to as DTL) was used as a component catalyst, and the same evaluation was performed.

(Comparative Example 1)
(B) Except not using a component, the composition was created by the method similar to Example 1, and the same evaluation was performed.

(Comparative Example 2)
(D) Except not using a component, the composition was created by the method similar to Example 1, and the same evaluation was performed.

(Comparative Example 3)
A composition was prepared in the same manner as in Example 1 except that 100 parts by weight of P6 obtained in Synthesis Example 6 was used as the component (A), and the same evaluation was performed.

  The results are summarized in Tables 3 and 4.

  As can be seen from Table 4, it can be seen that Examples 1-6 have better adhesion to difficult-to-adhere substrates as compared with Comparative Examples 1-3.

Claims (9)

  Reactive resin composition comprising an organic polymer (A) having an average of 0.8 or more reactive silicon groups in one molecule, a crosslinking regulator (B), a catalyst (C) and a filler (D) .   The reactive resin composition according to claim 1, wherein the average number of reactive silicon groups in the organic polymer (A) is 0.8 to 1.4 per molecule. Crosslinking regulator (B)
(Bi) a silicon compound having one silicon atom in the molecule and the total number of hydroxyl groups and hydrolyzable groups bonded to the silicon atom being one or two (here, hydrolyzable group Is a group that can react with moisture to form a silanol group with a silane atom),
(B-ii) The number of silicon atoms in the molecule is 2 to 20, the total number of hydroxyl groups and hydrolyzable groups bonded to any silicon atom in the molecule is 2 to 5, and each silicon atom In which the total number of hydroxyl groups and hydrolyzable groups bonded to the same silicon atom is 0 or 1, and (B-iii) a silicon compound R ⁴ —NH—R ¹ —Si of the following formula (1) R ² ) _z (R ³ ) _3-z (1)
(Wherein R ¹ is a branched or cyclic alkylene group, an arylene group, an alkalinene group, or an alkarylalkylene group, and when R ¹ has 4 or more carbon atoms, these groups are all One or more oxygen atoms or (poly) sulfide bonds may be included, R ² is an alkyl group having 1 to 6 carbon atoms, an aryl or alkaryl group having 5 to 20 carbon atoms. R ³ is a C1 to C6 alkoxy group or a C3 to C5 ketooximate group, R ⁴ is a hydrogen or hydrocarbon group, or an amine containing a nitrogen atom to which it is thermally attached to itself. A group that forms a group, and z is 0 or 1)
The reactive resin composition according to claim 1, which is a compound selected from the group consisting of:
(Alkalylene group means a divalent hydrocarbon group in which one of the bonds is on the aryl group and the other is on the alkyl group. The alkaryl group is on the aryl group. An aryl group having an alkyl group.)   The reactive resin composition in any one of Claims 1-3 which contain a 10-300 weight part filler (D) with respect to 100 weight part of an organic polymer (A).   The reactive resin composition according to any one of claims 1 to 4, wherein the main chain skeleton of the organic polymer (A) is an alkylene oxide polymer.   The number average molecular weight of an organic polymer (A) is 10,000-100,000. The reactive resin composition in any one of Claims 1-5.   It is adjusted so that the gel fraction based on the total amount of component (A), component (B) and component (C) of the cured product obtained by curing for 8 days at room temperature and normal humidity is less than 20% by weight. The reactive resin composition according to any one of claims 1 to 6.   The adhesive agent which uses the reactive resin composition in any one of Claims 1-7.   The adhesive according to claim 8, which is used for a difficult-to-adhere substrate.