JPH01252670A - Curable resin composition - Google Patents

Abstract

PURPOSE:To make it possible to obtain a high-strength cured rubberlike product having room temperature curability, good workability and excellent heat, water and weathering resistances, by constituting it from a saturated hydrocarbon polymer having SiOH groups and reactive silicon groups and an organic silicon polymer. CONSTITUTION:This curable resin composition is formed by mixing a saturated hydrocarbon polymer (of a number-average MW of 500-30000, desirably, 1000-15000), such as an isobutylene polymer, a hydrogenated polybutadiene polymer or an ethylene/propylene copolymer (A) having Si-bonded OH groups or hydrolyzable groups and reactive Si groups (i.e., an Si-containing group which can be crosslinked by forming siloxane bonds), for example, an isobutylene polymer having an -Si(CH3) (OCH3)2 group on each end, an organosilicon polymer (B) desirably, a liquid flowable silanol group-containing polysiloxane and a curing agent and other additives (C).

Description

[Detailed description of the invention] Industrial applications The present invention relates to a curable resin composition.

Conventional techniques and their problems A silicon atom-containing group (hereinafter referred to as a "reactive silicon group") that has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond is attached to the molecular end. Oxyalkylene polymers having the above-mentioned properties are already known and are used in large quantities because they have the interesting property of being cured by moisture even at room temperature and producing a rubber-like cured product.

However, the oxyalkylene polymer has a problem in that the cured product obtained by curing the polymer has insufficient properties such as heat resistance, water resistance, and weather resistance.

In order to improve such problems, for example, isobutylene polymers having reactive silicon groups at the molecular ends have been studied (see Japanese Patent Laid-Open No. 63-6041, etc.). However, the properties of cured products made from such isobutylene polymers, such as heat resistance, water resistance, weather resistance, and moisture barrier properties, are significantly improved compared to those of cured products made from the above-mentioned oxyalkylene polymers. However, in order for the cured product to have good rubber elasticity, it is necessary to lengthen the molecular chain, which inevitably results in a high viscosity of the above polymer, making it difficult to handle. Applications may be limited. Furthermore, if a low viscosity polymer is used to improve this drawback, the resulting cured product will inevitably have insufficient elongation properties.

Furthermore, since the cured product made from the isobutylene polymer has good moisture barrier properties, the supply of moisture necessary for curing may be insufficient, resulting in a problem of reduced curability.

Means for Solving the Problems The purpose of the present invention is to solve the above-mentioned problems of conventional curable resin compositions, to quickly harden with moisture in the air at room temperature, and to have heat resistance and water resistance. , a curable resin composition that has excellent weather resistance, etc., and can provide a rubber-like cured product with high strength and high elongation (low elastic modulus), and has low viscosity and good curability in workability. An object of the present invention is to provide a resin composition.

That is, the present invention relates to a curable resin composition containing (A) a saturated hydrocarbon polymer having at least one reactive silicon group, and (B) an organic silicone polymer.

In the present invention, component (A) is a saturated hydrocarbon polymer having at least one reactive silicon group.

Here, the reactive silicon group is not particularly limited, but representative examples include, for example, general formula (1) [wherein R1 and R2 both have 1 to 20 carbon atoms] Alkyl group with 6 to 20 carbon atoms, aryl group with 7 to 2 carbon atoms
0 aralkyl group or (R') 3 SiO-(R
' is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different), and R1 or R2
When two or more are present, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X's are present, they may be the same or different. a is 0.1.2 or 3
, b represents 0.1 or 2, respectively. Moreover, b in m pieces does not need to be the same. m represents O or an integer of 1 to 19. However, it is assumed that a+(sum of b)≧1 is satisfied. ] Examples include groups represented by the following.

The hydrolyzable group represented by X above is not particularly limited, and includes conventionally known hydrolyzable groups, specifically,
Examples include 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 an alkenyloxy group. Among these, hydrogen atoms, alkoxy groups, acyloxy groups, ketoximate groups,
An amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group are preferred, and an alkoxy group is particularly preferred from the viewpoint of mild hydrolysis and easy handling.

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

The number of silicon atoms forming the reactive silicon group may be one,
The number may be two or more, but in the case of silicon atoms connected by siloxane bonds or the like, the number may be up to about 20. In particular, general formula (2) [wherein R2, X and a are the same as above. A reactive silicon group represented by the following is preferred from the viewpoint of easy availability.

Further, specific examples of R1 and R2 in the above general formula (1) include alkyl groups such as methyl group and ethyl group,
Examples thereof include a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and a triorganosiloxy group represented by (R')3SiO-, where Rt is a methyl group, a phenyl group, etc. Among these, methyl group is particularly preferred.

At least one reactive silicon group, preferably 1.1 to 5 reactive silicon groups, should be present in one molecule of the saturated hydrocarbon polymer.

When the number of reactive silicon groups contained in the molecule is less than 1, curability becomes insufficient and it becomes difficult to exhibit good rubber elastic behavior.

The reactive silicon group may be present at the end of the saturated hydrocarbon polymer molecular chain, may be present inside, or may be present on both sides. In particular, when a reactive silicon group is present at the end of the molecular chain, the effective network chain amount of the saturated hydrocarbon polymer component contained in the finally formed cured product increases.
This is preferable from the viewpoint that it becomes easier to obtain a rubber-like cured product with high strength and high elongation.

The polymer forming the skeleton of the saturated hydrocarbon polymer having a reactive silicon group used as component (A) in the present invention is produced, for example, according to the method shown in (1) or (2) below.

(1) Ethylene, propylene, 1-butene, isobutylene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene,
An olefinic compound having 1 to 6 carbon atoms, such as hexene or vinylcyclohexane, is polymerized as a raw monomer. Here, the monomers may all be formed from the above-mentioned olefin compounds, and preferably 5 of the monomers include other monomers that are copolymerizable with the olefin compounds.
The content may be in the range of 0% by weight (hereinafter simply referred to as "%") or less, more preferably 30% or less, particularly preferably 10% or less. Examples of other monomers copolymerizable with olefin compounds include vinyl ethers, aromatic vinyl compounds, vinylsilanes, allylsilanes, and the like. Specific examples of such monomers include methyl vinyl ether, ethyl vinyl ether,
Examples include styrene, α-methylstyrene, vinyltrichlorosilane, vinylmethyldichlorosilane, allyltrichlorosilane, allyldimethylchlorosilane, and the like.

(2) Hydrogenating a homopolymer of a diene compound such as butadiene or isobutylene, or a copolymer of the above-mentioned olefin compound and a diene compound.

Even in the case of a polymer obtained by this method, monomer units derived from the other monomers may be present in the same proportion in the polymer.

In particular, ethylene-propylene copolymers, hydrogenated polybutadiene polymers, hydrogenated polyisoprene, and isobutylene polymers are preferred from the viewpoint of raw material availability and ease of handling.

The term saturated hydrocarbon polymer as used herein is a concept that means a polymer that does not substantially contain carbon-carbon unsaturated bonds other than aromatic rings.

In the isobutylene polymer, all of the monomer units may be formed from inbutylene units, and preferably 50% or less of monomer units copolymerizable with isobutylene, more preferably 50% or less of the monomer units copolymerizable with isobutylene. is less than 30%,
Most preferably, it may be contained in a range of 10% or less.

Examples of such monomer components copolymerizable with isobutylene include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinylsilanes, allylsilanes, and the like. More specifically, for example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexane, methyl vinyl ether, ethyl Vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyl Dichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1゜3,
3-Tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallyldimethoxysilane, diallyldimethylsilane, γ -methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and the like. When vinylsilanes or allylsilanes are used as monomers that are copolymerizable with isobutylene, the silicon content increases, and the number of groups that can act as silane strength and bubbling agents increases, improving the adhesiveness of the resulting composition. do.

Also, in hydrogenated polybutadiene polymers and other saturated hydrocarbon polymers, in addition to the main monomer, other monomers that can be copolymerized with the isobutylene polymer are also used. It may also contain body units.

In addition, the saturated hydrocarbon polymer used in the present invention preferably contains a small amount of monomer units that leave double bonds after polymerization, such as polyene compounds such as butadiene and isoprene, as long as the purpose of the present invention is achieved. may be contained in an amount of 10% or less, more preferably 5% or less, particularly preferably 1% or less.

The number average molecular weight of the saturated hydrocarbon polymer is 500 to
: Preferably about 30,000, especially 1,000 to
A liquid material with a fluidity of about 15,000 is preferred from the viewpoint of ease of handling.

Next, a method for producing a saturated hydrocarbon polymer having reactive silicon groups will be explained.

The introduction of reactive silicon groups into the above saturated hydrocarbon polymer is as follows:
This may be carried out by a known method, for example, adding active groups and unsaturated groups that are reactive with the functional groups to a saturated hydrocarbon polymer that has functional groups such as hydroxyl groups and anhydride groups at the terminal end or in the main chain. The reaction product may be reacted with an organic compound having the following, and then the resulting reaction product may be hydrosilylated by acting on a hydrosilane having a hydrolyzable group.

A method for introducing reactive silicon groups into isobutylene-based polymers and hydrogenated polybutadiene-based polymers will be specifically explained.

Among the above-mentioned isobutylene-based polymers having a reactive silicon group, isobutylene-based polymers having a reactive silicon group at the end of the molecular chain are produced by a polymerization method called the Vinifer method (a specific method using a polymerization method called an Inifer method that uses both an initiator and a chain transfer agent). It can be produced using a terminally functional type, preferably all terminally functional type isobutylene polymer obtained by a cationic polymerization method using a compound of Such a manufacturing method is known, for example, from Japanese Patent Application Laid-open No. 6
Publications such as Publication No. 3-6041 and Publication No. 63-6003, as well as Japanese Patent Application No. 62-90078 and No. 62-179733.
No. 62-194838.

Isobutylene polymers having reactive silicon groups within their molecular chains are produced by adding vinylsilanes or allylsilanes having reactive silicon groups to a monomer mainly composed of isobutylene, and copolymerizing the mixture. .

Furthermore, during polymerization to produce isobutylene-based polymers having reactive silicon groups at the molecular chain ends, the main component isobutylene is copolymerized with vinylsilanes or allylsilanes having reactive silicon groups, and then the above-mentioned polymers are added to the ends of the polymers. By introducing reactive silicon groups by this method, an isobutylene polymer having reactive silicon groups at the terminals and inside the molecular chain is produced.

Specific examples of vinylsilanes and allylsilanes having reactive silicon groups include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, divinyldichlorosilane, divinyldimethoxysilane, allyltrichlorosilane, Allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane,
diallyldichlorosilane, diallyldimethoxysilane,
Examples include γ-methacryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropylmethyldimethoxysilane.

As mentioned above, since the isobutylene-based polymer having a reactive silicon group does not substantially contain unsaturated bonds other than aromatic rings in the molecule, the composition of the present invention containing the isobutylene-based polymer is The weather resistance of the cured product is significantly improved compared to compositions containing conventional rubber polymers such as organic polymers and oxyalkylene polymers having unsaturated bonds. In addition, since the isobutylene polymer is a hydrocarbon polymer, it has excellent moisture barrier properties and water resistance, and has excellent adhesion performance to various inorganic substrates such as glass and aluminum, and has low moisture permeability. Can become a cured product.

The hydrogenated polybutadiene polymer or hydrogenated polyisoprene can be obtained by, for example, first converting the hydroxyl group of the terminal hydroxy-hydrogenated polybutadiene-based polymer or terminal hydroxy-hydrogenated polyisoprene into an oxymetal group such as 10Na or -OK.
In addition, general formula (3)% formula% (3) [wherein Y is a halogen atom such as a chlorine atom or an iodine atom, R
7 is -R8-1-R8-QC- or -Re -C- (where R8 is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably an alkylene group, a cycloalkylene group, an arylene group, an alkylene group) Particularly preferred are divalent groups selected from 1 to 10 hydrocarbon groups). ] By reacting the organic halogen compound represented by (also referred to as "terminal olefin hydrogenated polyisoprene") is produced.

Methods for converting the terminal hydroxyl groups of terminal hydroxy-hydrogenated polybutadiene polymers and terminal hydroxy-hydrogenated polyisoprene into oxymetal groups include alkali metals such as sodium and potassium; metal hydrides such as sodium hydride; and sodium methoxide. Examples include a method of reacting a metal alkoxide such as; a caustic alkali such as caustic soda or caustic potash with the terminal hydroxyl group.

According to the above method, a terminal olefin-hydrogenated polybutadiene polymer having approximately the same molecular weight as the terminal hydroxy-hydrogenated polybutadiene polymer used as a starting material can be obtained, but it is desirable to obtain a polymer with a higher molecular weight. in case of,
Before reacting the organic halogen compound of general formula (3),
Methylene chloride, bis(chloromethyl)benzene, bis(
The molecular weight can be increased by reacting a polyvalent organic halogen compound containing two or more halogen atoms in one molecule, such as chloromethyl) ether, with the above polymer, and then the organic halogen of general formula (3) can be reacted with the above polymer. If you react with a compound,
Hydrogenated polybutadiene polymers having higher molecular weight and having olefin groups at the terminals can be obtained.

As the organic halogen compound of the above general formula (3), a wide variety of conventionally known compounds can be used. Specifically, allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) Benzene, allyl (chloromethyl) ether,
Examples include allyl(chloromethoxy)benzene, 1-butenyl(chloromethyl)ether, 1-hexenyl(chloromethoxy)benzene, and allyloxy(chloromethyl)benzene. Among these, allyl chloride is preferred because it is inexpensive and has high reactivity.

The introduction of a reactive silicon group into the above-mentioned terminal olefin-hydrogenated polybutadiene polymer or terminal olefin-hydrogenated polyisoprene can be carried out in the same way as in the case of isobutylene polymers having reactive silicon groups at the molecular chain ends, for example, using the general formula (1). A hydrosilane compound in which a hydrogen atom is bonded to a group represented by the formula, preferably represented by the general formula (4) [wherein R2, X and a are the same as above.

] is carried out by carrying out an addition reaction using a platinum-based catalyst.

As the hydrosilane compound in which a hydrogen atom is bonded to the group represented by the above general formula (1), a wide variety of conventionally known compounds can be used, and specific examples include trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane. Halogenated silanes; alkoxysilanes such as ethoxysilane, triethoxysilane, methyljethoxysilane, methyldimethoxysilane, and phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; bis( Examples include ketoximate silanes such as dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane. Among these, halogenated silanes and alkoxysilanes are particularly preferred.

The saturated hydrocarbon polymer having the above-mentioned reactive silicon group has 1
Each species may be used alone or two or more species may be used in combination.

In the present invention, the heat resistance of component (A) gives a rubber-like cured product with good heat resistance, weather resistance, water resistance, etc., high strength and high elongation, but has the problem of high viscosity and difficulty in handling. In order to lower the viscosity and make it easier to handle without reducing weather resistance, strength, elongation properties, etc., to speed up curing, and to eliminate surface tack (stickiness) after curing, the organic A silicone polymer is blended.

In the present invention, the organosilicon polymer is a polymer whose main skeleton is a siloxane bond in which silicon atoms having an organic group are alternately bonded to oxygen atoms, and a representative example thereof is the general formula (5) [Formula In the formula, R3, R4, R5 and Rθ are the same or different and represent a non-hydrolyzable organic group having 1 to 12 carbon atoms or X (X is the same as above), and at least one of R3 to R6 is It is a non-hydrolyzable organic group, R5 and Rθ may be combined with each other to form a ring, and n is an integer of 1 to 5000, preferably 5 to 100. ] Polymers represented by:

Here, specific examples of non-hydrolyzable organic groups having 1 to 12 carbon atoms include alkyl groups such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, and benzyl group. Examples include aralkyl groups. Further, specific examples of X include the same groups as the specific examples of X in the above general formula (1). Furthermore, n R3s or n R4s in the general formula (5) do not need to be the same group.

Examples of the organosilicon polymer used in the present invention include Japanese Patent Publication No. 59-38987, Japanese Patent Application Publication No. 55-60558, Japanese Patent Publication No. 55-78055, Japanese Patent Publication No. 57-14514.
Publication No. 7, Publication No. 57-190043, Publication No. 59-25
No. 837, No. 61-23643, r9586
Organic silicone polymers disclosed in pages 721 to 727 of "Chemical Products" (published by Kagaku Kogyo Nippo on January 30, 1985) can be widely used, and more specifically, dimethylsilicone oil, methyl Examples include silicone oils such as phenyl silicone oil; organopolysiloxanes having organo groups such as the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. In addition, these may be used as they are, or alkyd resins, epoxy resins, polyester resins, urethane resins, acrylic resins, polyethylene oxide, polypropylene oxide,
It may also be used as a copolymer such as a block copolymer or a graft copolymer comprising an organic polymer such as ethylene oxide-propylene oxide copolymer, polybutylene oxide, or polytetrahydrofuran. In addition, silicone oils and organopolysiloxane copolymers with reactive silicon groups such as the reactive silicon group represented by the general formula (1), and silicone oils with silicon atoms such as hydrogen atoms in methylhydrogen silicone oils may also be used. Organopolysiloxanes having a hydrolyzable group or hydroxyl group bonded to are also included in the organosilicon polymer of the present invention.

Among the above-mentioned organosilicon polymers, those having liquid to fluidity are preferred because they are easy to handle.

In addition, the organosilicon polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom also reacts with the saturated hydrocarbon polymer (A) during curing of the composition, so the organosilicon polymer may bleed. This is preferable because it has the advantage of not reducing the elastic modulus or elongation too much even if used in large quantities, and preventing surface tack (stickiness).

The above copolymer of organopolysiloxane and organic polymer can be synthesized, for example, by the method described in JP-A-57-145147, etc., but is not limited to these methods.

Among the above organopolysiloxanes, polysiloxanes having two or more silanol groups are particularly preferred. If such a polysiloxane is used, it is particularly excellent in deep curing properties (when obtaining a thick cured product, curing progresses easily inside the cured product), and the cured product also has excellent weather resistance and heat resistance. It is possible to obtain a curable resin composition that can impart the following properties.

As such polysiloxane, a wide variety of commercially available polysiloxanes can be used, but if it is particularly compatible with the above component (A), a cured product with more stable performance can be obtained. It is desirable to use a material with a relatively low molecular weight, that is, a material having 50 or less silicon atoms in one molecule. Specific examples of such polysiloxanes are as follows.

[In each of the above formulas, Me is a methyl group and pH is a phenyl group, and the same applies to the following examples. ]

The above organosilicon polymers may be used alone or in combination of two or more.

The total composition of the above-mentioned organosilicon polymer varies depending on the desired viscosity of the resulting composition, the type of organosilicon polymer used, etc., but cannot be generalized;
The organic silicone polymer is usually added in an amount of about 1 to 1,000 parts, preferably 10 to 1,000 parts per part (hereinafter simply referred to as "parts").
It is preferable to mix the two in an amount of about 150 parts.

When using a polysiloxane having two or more silanol groups as the organosilicon polymer, the number of hydroxyl groups bonded to the silicon atom of the polysiloxane is 0.1 to 8 per 1 hydroxyl group of component (A). Preferably 0.3~
It is preferable to mix the two so that the number is about 4. In the present invention, it is particularly preferable to blend about 20 to 120 parts of the above polysiloxane per 100 parts of component (A>
It is most preferable to mix about 100 parts. If the amount of the polysiloxane blended is extremely small, a resin composition with insufficient deep curability will be obtained, which is not preferable. On the other hand, if the amount of the polysiloxane blended is extremely large, the tensile properties of the resulting cured product will deteriorate, which is not preferable.

The cured product obtained from the composition of the present invention has good weather resistance, heat resistance, water resistance, etc., which the cured product from the component (A) has, and maintains excellent properties such as high strength and high elongation. Moreover, due to the action of component (B), the viscosity of the composition is reduced, resulting in good workability, and the surface tackiness of the cured product (
Stickiness) can be prevented.

In the present invention, the above organosilicon polymer is used in place of a solvent for the purpose of adjusting the reaction temperature, adjusting the viscosity of the reaction system, etc. when introducing reactive silicon groups into a saturated hydrocarbon polymer. You can also.

It is desirable that the composition of the present invention contains a curing catalyst that promotes the silanol condensation reaction. As such a curing catalyst, a wide variety of conventionally known catalysts can be used. Specific examples include titanate esters such as tetrabutyl titanate and tetrapropyl titanate; tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, and tin naphthenate; dibutyltin oxide and phthalic acid. Reactants with esters: dibutyltin diacetylacetonate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoquine aluminum ethyl acetoacetate; zirconium tetraacetylacetonate, titanium tetraacetylacetonate, etc. Chelate compounds; lead octylate; butylamine, octylamine, dibutylamine, monoethanolamine, jetanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylene diamine, Triethylenediamine, guanidine, diphenylguanidine, 2,4.6-
Amine compounds such as tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo(5,4,O)undecene-7 (DBU), or these salts with carboxylic acids, etc.; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products between excess polyamines and epoxy compounds; silane coupling agents having amino groups, such as γ-aminopropyl Examples include silanol condensation catalysts such as trimethoxysilane and N-(β-aminoethyl)aminopropylmethyldimethoxysilane, as well as 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. When a curing catalyst is used, the amount of the curing catalyst is (A
) The amount is usually about 0.1 to 20 parts, preferably about 1 to 10 parts, per 100 parts of the component.

If the amount of curing catalyst blended with respect to component (A) is too small,
Both are unfavorable, since the curing speed of the resulting resin composition will be slow, and if the amount is too high, the physical properties such as tensile properties of the resulting cured product will deteriorate.

The composition of the present invention further includes an adhesion improver, a physical property regulator,
Storage stability improver, plasticizer, filler, anti-aging agent, ultraviolet absorber, metal deactivator, anti-ozonant, light stabilizer, amine-based radical chain inhibitor, phosphorus-based peroxide decomposer, Various additives such as lubricants, pigments, and blowing agents can be added as appropriate.

Here, as the adhesion improver, commonly used adhesives, silane coupling agents such as aminosilane compounds and epoxysilane compounds, and other compounds can be used. Specific examples of such adhesion improvers include phenol resin, epoxy resin, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropylmethyldimethoxysilane, coumaron-indene resin, rosin ester resin, Terpene-phenolic resin, α
Examples include -methylstyrene-vinyltoluene copolymer, polyethylmethylstyrene, alkyl titanates, and aromatic polyisocyanates. When blending an adhesion improver, the blending amount is Component (A) and (B).
It is preferably about 1 to 50 parts per 100 parts of the total amount of ingredients.
About 5 to 30 parts is more preferable.

Examples of storage stability improvers include compounds in which a hydrolyzable group is bonded to a silicon atom, ortho-organic acid esters, and the like. Specific examples of such storage stability improvers include methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, ethyltrimethoxysilane, dimethyljethoxysilane, trimethylisobutoxysilane, and trimethyl(n-butoxy)silane. ,
Examples include n-butyltrimethoxysilane and methyl orthoformate. When blending a storage stability improver, the blending amount is preferably about 0.5 to 20 parts, and 1 to 20 parts, per 100 parts of the total amount of components (A) and (B).
About 10 parts is more preferable.

The plasticizer is not particularly limited either, and any commonly used plasticizer can be used, but those having good compatibility with the various components contained in the composition of the present invention are preferred. Specific examples of such plasticizers include polybutene,
Hydrogenated polybutene, ethylene-α-olefin oligomer, α-methylstyrene oligomer, biphenyl, triphenyl, triaryl dimethane, alkylene triphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyldiphenyl, partially hydrogenated terphenyl, paraffin oil , naphthenic oil, atactic polypropylene, and other hydrocarbon compounds; chlorinated paraffins; dibutyl phthalate, dibutyl phthalate, di(2-ethylhexyl) phthalate, butyl benzyl phthalate, butyl phthalyl butyl glycolate, and other phthalic acid esters; Non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate; polyalkylene glycol esters such as diethylene glycol benzoate and triethylene glycol dibenzoate; phosphoric acid esters such as tricresyl phosphate and tributyl phosphate, etc. It will be done. These may be used alone or in combination of two or more. Among these, hydrocarbon compounds that do not have unsaturated groups (specifically hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthenic oil, acidic polypropylene, etc.) are blended into the composition of the present invention. It is preferable because it has good compatibility with the various components used in the composition, has a small effect on the curing rate of the composition, provides a cured product with good weather resistance, and is inexpensive. These plasticizers may be used in place of a solvent for the purpose of adjusting the reaction temperature, adjusting the viscosity of the reaction system, etc. when introducing reactive silicon groups into a saturated hydrocarbon polymer. When blending a plasticizer, the blending amount is the total amount of components (A) and (B) 10
Per 0 parts, about 10 to 500 parts is preferable, and 20 to 30 parts.
About 0 parts is more preferable.

Specific examples of fillers include wood flour, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut, grain flour, rice flour, graphite, diatomaceous earth, white clay,
Examples include humic silica, precipitated silica, silicic anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, fine aluminum powder, flint powder, and zinc powder. Among these fillers, fillers having thixotropic properties such as precipitated silica, humic silica, and carbon black, calcium carbonate, titanium oxide, and talc are preferred.

When blending a filler, the blending amount is preferably about 10 to 500 parts, more preferably about 20 to 300 parts, based on a total of 11,100 parts of components (A) and (B).

Examples of the anti-aging agent include commonly used anti-aging agents, such as sulfur-based anti-aging agents, radical inhibitors, and ultraviolet absorbers.

Examples of sulfur-based anti-aging agents include mercaptans, mercaptan salts, sulfides including sulfide carboxylic acid esters and hindered phenol sulfides, polysulfides, dithiocarboxylic acid salts, thioureas, thiophosphates, and sulfonium Examples include compounds, thioaldehydes, thioketones, mercaptals, mercapdols, monothio acids, polythio acids, thioamides, sulfoxides, and the like. Specific examples of such sulfur-based anti-aging agents include mercaptans2.
-Mercaptobenzothiazole, zinc salt of 2-mercaptobenzothiazole which is a mercaptan salt, 4,4'-thio-bis(3-methyl-6-
t-butylphenol), 4,4'-thio-bis(2
-methyl-6-t-butylphenol), 2.2' -
Thio-bis(4-methyl-6-t-butylphenol)
, bis(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, terephthaloyl di(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine, 2,2'-thio-bis (4
-octylphenol) nickel, dilaurylthiodipropionate, distearylthiodipropionate, simiristylthiodipropionate, ditridecylthiodipropionate, distearyl β, β′-thiodibutyrate, lauryl-stearylthiodipropionate Nate, 2
,2-thio[diethyl-bis-3-(3゜5-di-t-
Butyl-4-hydroxyphenol)propionate]
, polysulfides such as 2-benzothiazole disulfide, dithiocarboxylic acid salts such as tinc dibutyl dithiocarbamate, tinc diethyldithiocarbamate, nickel dibutyl dithiocarbamate, tinc di-n
-butyldithiocarbamate, dibutylammonium dibutyldithiocarbamate, tinquethyl phenyl dithiocarbamate, tincque dimethyldithiocarbamate, thioureas such as 1-butyl-3-oxy-diethylene-2-thiourea, di-0-tolyl-thiourea, ethylenethiourea , trilauryltrithiophosphate, which is a thiophosphate, and the like. When used in the composition of the present invention, such a sulfur-based anti-aging agent can significantly prevent decomposition and deterioration of the main chain due to heat, and reduce surface tack (stickiness).
The occurrence of such problems can be prevented.

Examples of the radical inhibitor include 2,2-methylene-bis(4-methyl-6-t-butylphenol), tetrakis[methylene-3-(3°5-di-t-butyl-
Phenol-based radical inhibitors such as 4-hydroxyphenyl)propionate] methane, phenyl-β-naphthylamine, α-naphthylamine, N, N'-5e
Examples include amine radical inhibitors such as e-butyl-p-phenylenediamine, phenothiazine, and N,N'-diphenyl-p-phenylenediamine.

Examples of the ultraviolet absorber include 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, bis(2,2,6,6-tetramethyl-4-piperidine) sebacate, etc. can be mentioned.

When blending the above anti-aging agent, the blending amount is (A)
It is preferably about 0.1 to 20 parts per 100 parts of the component, and 1
About 10 parts is more preferable.

Effects of the Invention The curable resin composition of the present invention has good workability and can yield a cured product with significantly excellent weather resistance, heat resistance, water resistance, strength, elongation properties, etc. Further, when a polysiloxane having two or more silanol groups is used, there is an advantage that the composition has particularly excellent deep curability. Therefore, the composition of the present invention can be suitably used as a sealant, adhesive, paint, waterproofing agent, spray agent, molding material, casting rubber material, and the like.

EXAMPLES In order to further clarify the present invention, production examples, working examples, and comparative examples are listed below.

Production Example 1 Isobutylene having a molecular weight of about 5,000 and having isopropenyl groups at both ends at a ratio of about 92% was produced by polymerizing isobutylene with p-dicumyl chloride using boron trichloride as a catalyst and then dehydrochlorinating it. Weighed 200 g of the system polymer and 10 g of toluene into a 500 mQ four-hole flask, and
The mixture was degassed under reduced pressure at 0°C for 2 hours. Next, 120 mg of hebutane and 11.0 mg of methyldichlorosilane were dried at room temperature under a nitrogen atmosphere.
After adding 5 g and 0.1 m of chloroplatinic acid catalyst solution (2 (a solution in which 201 g of H2PtCQs.6H was dissolved in 9 g of 1,2-dimethoxyethane and 1 g of ethanol), the reaction was carried out at 90°C for 12 hours.

When the amount of residual isopropenyl groups in the isobutylene polymer in the reaction solution was quantified by IR spectrometry, it was found that almost none remained.

Next, 21.2 g of methyl orthoformate and 6.4 g of methanol
g was added thereto, and the mixture was reacted at 70°C for 3 hours.

At this point, the pH of the reaction system was approximately 7, making it neutral.

After distilling off the volatile components under reduced pressure, 50 volumes of hexane were added to the remaining components and thoroughly stirred, and insoluble components were removed by filtration.

Hexane was distilled off from the synovial fluid, and -8i (CH
3) An isobutylene polymer having two (OCH3) groups was obtained.

As a result of NMR analysis of the obtained polymer, it was found that -8i (CH3)(OCH3)2 groups were introduced into about 80% of the molecular ends.

Production Example 2 Terminal hydroxy hydrogenated polybutadiene (Polytail HA,
176 g of a methanol solution of sodium methoxide (concentration 28%) was added to 800 g (manufactured by Mitsubishi Kasei Kogyo Kan), and an oxymetalation reaction was carried out for about 5 hours while devolatilizing at 130°C. Then 3-chloro-2-methyl-1-propene99. 1 g was added and the mixture was reacted at 90° C. for 3 hours and then purified.

When the obtained liquid polymer was analyzed by NMR method and GPC method, it was found to be a polymer having an average molecular weight of 3500 and having isopropenyl groups introduced into 76% of all terminals.

40 g of this polymer 13.5 μQ of chloroplatinic acid catalyst solution (
0.2 mol/Q isopropyl alcohol solution of H2PtCQs 6H20) and methyldichlorosilane 46
After reacting at 85°C for 8 hours in the same manner as in Production Example 1, 8.7 tsp of methyl orthoformate and 3 g of methanol were added.
．． 2- was added and reacted at 70°C for 3 hours.

When the amount of residual isopropenyl groups in the reaction solution was determined by IR spectroscopy, it was found that almost no isopropenyl groups remained. Furthermore, when the reactive silicon groups were quantified by NMR method, it was found that almost 100% of the isopropenyl group at the end of the molecule was composed of (CH30)2Si, (CH3)Ct(2CH(C
H3) It was found that it was a CH20- group.

Manufacturing example 3 Terminal hydroxy hydrogenated polyisoprene (EPR).

48 g of t-butoxypotassium and 200 mQ of tetrahydrofuran were added to 300 g (manufactured by Idemitsu Petrochemical Co., Ltd.) and heated at 50°C for 1 hour to perform an oxymetalation reaction. Then, allyl chloride 47 precepts were added and the mixture was heated to 50°C.
After reacting for 1 hour, the mixture was purified.

When the obtained liquid polymer was analyzed by NMR method and GPC method, it was found to be a polymer having an average molecular weight of 2500 in which allyl groups were introduced into 75% of all terminals.

100 g of this polymer and 5 g of toluene were weighed into a 4-bottle flask and degassed under reduced pressure at 90° C. for 2 hours. Next, 57μQ of chloroplatinic acid catalyst solution was added at room temperature under nitrogen atmosphere.
After adding (0.19 mol/Q ethanol solution of H2PtCQs.6H20), 14.6 g of methyldimethoxysilane was added dropwise while heating, and the mixture was reacted at 70° C. for 3 hours.

When the amount of residual isopropenyl groups in the reaction solution was determined by IR spectroscopy, it was found that almost no isopropenyl groups remained. Furthermore, when the reactive silicon groups were quantified by NMR method, almost 100% of the isopropenyl group at the end of the molecule was (CH30)2Si(CH3)CH2CH2CH
It was found that there were 20 groups.

Examples 1 to 8 and Comparative Examples 1 to 2 The components shown in Table 1 were blended in the proportions shown in Table 1 to prepare homogeneous compositions, and the viscosity was measured. The results are shown in Table 1.

Next, the obtained composition was cast into a sheet having a thickness of 3III, cured at room temperature for 4 days, and then aged at 50° C. for 4 days.

The tack, heat resistance, and weather resistance of the obtained cured sheet were evaluated. Further, the curing time was determined by observing the curing state of another sample at 23°C. The results are shown in Table 2 below.

1) PS 340.5...terminated silanol polydimethylsiloxane. Made by Chisso ■.

2) PS 084... terminal diphenylsilanol polydimethyldiphenylsiloxane. Made by Chisso ■.

3) PS 080...Terminal silanol polydiphenylsiloxane. Manufactured by Chisso Corporation.

4) The amount of silanol in the polysiloxane is equivalent to the methoxysilyl group in the polymer.

5) The amount of silanol in the polysiloxane is 1.2 times equivalent to the methoxysilyl group in the polymer.

Claims (8)

[Claims] (1) (A) A saturated hydrocarbon polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon atom-containing group that can be crosslinked by forming a siloxane bond, and (B ) A curable resin composition containing an organic silicone polymer. (2) The above silicon atom-containing group has a general formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R^1 and R^2 both have a carbon number of 1 to 20
Alkyl group, aryl group having 6 to 20 carbon atoms, 7 carbon atoms
~20 aralkyl group or (R')_3SiO- (R' is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R's may be the same,
(which may be different), and when two or more R^1 or R^2 are present,
They may be the same or different. X
represents a hydroxyl group or a hydrolyzable group, and when two or more X's are present, they may be the same or different. a represents 0, 1, 2 or 3, and b represents 0, 1 or 2, respectively. Also, b in m number of ▲mathematical formulas, chemical formulas, tables, etc.▼ does not need to be the same. m is 0 or 1-1
Indicates an integer of 9. However, it is assumed that a+(sum of b)≧1 is satisfied. ] The composition according to claim 1, which is a group represented by the following. (3) Claim (2), wherein X in general formula (1) is a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, or an alkenyloxy group. Composition of. (4) The composition according to claim (2), wherein X in general formula (1) is an alkoxy group. (5) The saturated hydrocarbon polymer is at least one selected from the group consisting of isobutylene polymers, hydrogenated polybutadiene polymers, hydrogenated polyisoprene, and ethylene propylene copolymers. Composition of. (6) The number average molecular weight of the above polymer is 500 to 30,000
The composition according to claim (5). (7) The above organosilicon polymer has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ [In the formula, R^3, R^4, R^5 and R^6 are the same or different and have a carbon number of 1 ~12 non-hydrolyzable organic groups or X
(X is a hydroxyl group or a hydrolyzable group), and R^3 to R^
At least one of the groups in 6 is a non-hydrolyzable organic group. Further, R^5 and R^6 may be combined with each other to form a ring. n represents an integer of 1 to 5,000. ] The composition according to claim (1), which is a polymer represented by: (8) The composition according to claim (1), wherein the organosilicon polymer is a polysiloxane having two or more silanol groups.