JPH10237116A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition, capable of providing a cured product having improved weather-resistant adhesion to various glasses and having high mechanical characteristics (hardness), by making the composition include a saturated hydrocarbon-based polymer having reactive silicon groups and a specify compound therein. SOLUTION: This composition contains (A) a saturated hydrocarbon-based polymer, capable of providing a cured product having 2-6kg/cm<2> value of tensile stress at 50% elongation and having silicon-containing groups, having hydroxyl group or a hydrolyzable group bound to silicon group (e.g. an alkoxy group) and cross-linkable by forming a siloxane bond and represented by the formula [R<1> and R<2> are each a 1-20C alkyl, etc.; X is the hydroxyl group or the hydrolyzabl group; (a) is 0, 1, 2 or 3; (b) is 0, 1 or 2; (m) is 0 or 1-19:] (e.g. polyisobutylene) and (B) a photopolymerizable substance having 4 or more functional groups polymerizable by irradiation of light [e.g. (meth)acryloyl groups] in one molecule [e.g. pentaerythritol tetra(meth)acrylate]. The component B is preferably contained in an amount of 0.1-20pts.wt. based on 100pts.wt. component A having 7,000-15,000 molecular weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition having improved weather resistance and hardness of a cured product, which is useful as a sealing material or an adhesive for double glazing and for construction.

[0002]

2. Description of the Related Art At least one silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond (hereinafter referred to as "reactive silicon group"). It is known that a saturated hydrocarbon polymer has an interesting property that even at room temperature, it is crosslinked by the formation of a siloxane bond accompanied by a hydrolysis reaction of a reactive silicon group due to moisture or the like, and a rubber-like cured product is obtained. ing. For this reason, it is effective to use as a sealing material for double glazing or an elastic sealing material for buildings.

On the other hand, a sealing material used around a glass such as a sealing material for a double-glazed glass is required to be particularly excellent in weather resistance, but the above-mentioned saturated hydrocarbon polymer containing a reactive silicon group is required. When used, the weather resistance was slightly inadequate. Recently, heat ray reflective glass having high heat insulating properties has been increasingly used, and there has been a problem that the weather resistance to the heat ray reflective glass is particularly insufficient.

Unlike architectural sealing materials that require low modulus and high elongation, sealing materials for double glazings have high modulus and high enough to support the weight of the glass.
It is necessary to have a high hardness, when using a saturated hydrocarbon polymer containing a reactive silicon group described above,
There was a problem that the mechanical properties (hardness) were insufficient.

[0005]

SUMMARY OF THE INVENTION The present invention improves the weather resistance of a curable composition containing a saturated hydrocarbon polymer having a reactive silicon group as a main component to various types of glass, and improves the mechanical properties of the cured product. (Hardness).

[0006]

[Means for Solving the Problems] The present inventors have conducted intensive studies to solve such problems, and as a result, by adding a specific compound to the polymer, the curability of the composition has been improved. The above problem was solved by finding that the weather resistance to various adherends could be improved and the physical properties of the cured product (hardness, etc.) could be improved without adverse effects such as reduction, and the present invention was completed. Was.

That is, the present invention relates to (A) a cured product of 50
% Of a reactive hydrocarbon group having at least one reactive silicon group having a value of ² to 6 kgf / cm ² , and (B) a functional group capable of being polymerized by light irradiation in one molecule. It relates to a curable composition characterized by containing the photopolymerizable substance having the above, especially,
(A) The value of the 50% tensile stress of the cured product is 2 to 6 kgf /
It is cm ^2, and containing at least one reactive silicon group in its molecule, a molecular weight relative to the saturated hydrocarbon polymer 100 parts by weight of 7000～15,000, polymerized by irradiation (B) light Acrylates or methacrylates having 4 or more functional groups per molecule in a molecule of 0.1 to 2
The present invention relates to a curable composition having improved weather resistance, characterized by containing 0 parts by weight.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The saturated hydrocarbon-based polymer having a reactive silicon group used in the present invention is a polymer substantially containing no carbon-carbon unsaturated bond other than the aromatic ring, for example, polyethylene, polypropylene, polyisobutylene, hydrogenated Examples thereof include polybutadiene and hydrogenated polyisoprene. As the reactive silicon group, general formula (1),

[0009]

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(Wherein R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or (R ′) ₃ SiO- (R 'is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), and X is a triorganosiloxy group.
Each is independently a hydroxyl group or a hydrolyzable group. Further, a is 0, 1, 2, 3, and b is 0,
It is either 1 or 2, and a and b do not become 0 at the same time. M is 0 or an integer of 1 to 19)
And the group represented by

Examples of the hydrolyzable group include groups generally used such as 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. Can be Among these, an alkoxy group, an amide group and an aminooxy group are preferred, but an alkoxy group is particularly preferred because of its mild hydrolyzability and easy handling.

A hydrolyzable group or a hydroxyl group can be bonded to one silicon atom in the range of 1 to 3 (a + Σ
b) 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. The number of silicon atoms forming the reactive silicon group is one or more. In the case of silicon atoms linked by a siloxane bond or the like, the number is preferably 20 or less. In particular, the general formula (2)

[0013]

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(Wherein R ² , X and a are as defined above) are preferred because they are easily available. The number of reactive silicon groups in one molecule of the saturated hydrocarbon-based polymer is one or more, preferably 1.1 to 5. If the number of reactive silicon groups contained in the molecule is less than one, the curability may be insufficient and good rubber elasticity may not be obtained.

The reactive silicon group may be at the terminal or inside the molecular chain of the saturated hydrocarbon polymer, or may be at both. In particular, when the reactive silicon group is located at the molecular end, the amount of the effective network chain of the saturated hydrocarbon-based polymer component contained in the finally formed cured product is increased, so that a high-strength, high-elongation rubber-like It is preferable in that a cured product is easily obtained.

These saturated hydrocarbon polymers having a reactive silicon group can be used alone or in combination of two or more. The polymer constituting the skeleton of the saturated hydrocarbon polymer having a reactive silicon group used in the present invention is mainly composed of (1) an olefinic compound having 1 to 6 carbon atoms such as ethylene, propylene, 1-butene, isobutylene and the like. It can be obtained by a method of polymerizing as a monomer, (2) homopolymerizing a diene compound such as butadiene, isoprene, or the like, or copolymerizing the above olefin compound and then hydrogenating. Isobutylene-based polymers and hydrogenated polybutadiene-based polymers are preferred because a functional group can be easily introduced into the terminal, the molecular weight can be easily controlled, and the number of terminal functional groups can be increased.

In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units,
The monomer unit having copolymerizability with isobutylene is contained in the isobutylene-based polymer in an amount of preferably 50% or less (% by weight, the same applies hereinafter), more preferably 30% or less, particularly preferably 10% or less. Is also good. Examples of such monomer components include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, allyl silanes, and the like. Such copolymer components include, for example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene,
Vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyl Trimethylsilane, divinyldichlorosilane, 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 vinyl silanes or allyl silanes are used as monomers copolymerizable with isobutylene, the silicon content increases and the number of groups that can act as a silane coupling agent increases. The adhesion is improved. In the hydrogenated polybutadiene-based polymer and other saturated hydrocarbon-based polymers, as in the case of the isobutylene-based polymer, other monomer units are contained in addition to the main monomer unit. You may.

The saturated hydrocarbon polymer having a reactive silicon group used in the present invention includes a double bond after polymerization, such as a polyene compound such as butadiene and isoprene, as long as the object of the present invention is achieved. May be contained in a small amount, preferably 10% or less, more preferably 5% or less, and particularly preferably 1% or less. The number average molecular weight of the saturated hydrocarbon polymer, preferably the isobutylene polymer or the hydrogenated polybutadiene polymer is from 7,000 to
It is preferably about 15,000, especially 8,000.
Those having a liquid or fluidity of about 0 to 12,000 are preferred from the viewpoint of easy handling.

A saturated hydrocarbon polymer, preferably an isobutylene polymer or a hydrogenated polybutadiene polymer, has a number average molecular weight per reactive silicon group, that is, a number average molecular weight (Mn) and a number per molecule. The ratio (Mn / Fn) of the number of reactive silicon groups (Fn) is 4000 to 70
Those within the range of 00 are preferred. This is because the value of the 50% tensile stress of the cured product of the base polymer is also determined by the number average molecular weight per reactive silicon group, that is, the molecular weight between crosslinking points. When the number average molecular weight per reactive silicon group is larger than 7000, the value of 50% tensile stress may not be ² kgf / cm ² or more, and when the number average molecular weight per reactive silicon group is less than 4000 Has a value of 50% tensile stress of 6 kgf / cm ²
The following may not be the case.

Next, a method for producing a saturated hydrocarbon polymer having a reactive silicon group will be described. Among the isobutylene-based polymers having a reactive silicon group, an isobutylene-based polymer having a reactive silicon group at a molecular chain terminal is a polymerization method called an inifer method (a specific method using both an initiator and a chain transfer agent called inifer). (Cationic polymerization method using a compound), and can be produced using a terminal-functional isobutylene-based polymer, preferably an all-terminal-functional isobutylene-based polymer. For example, polyisobutylene having a terminal unsaturated group was obtained by a dehydrohalogenation reaction of this polymer or an unsaturated group introduction reaction into the polymer as described in JP-A-63-105005. Later, the general formula

[0022]

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(Wherein R ¹ , R ² , X, a and b are the same as described above) (this compound has a hydrogen atom in the group represented by the general formula (1)) A bonded compound), preferably a compound of the general formula

[0024]

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(Wherein, R ² , X and a are the same as described above) to form a reactive silicon group by performing an addition reaction called hydrosilylation reaction using a platinum catalyst. There is a method of introducing into the coalescence. Examples of the hydrosilane compound include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; and trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, and phenyldimethoxysilane. Alkoxysilanes; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; and ketoximesilanes such as bis (dimethylketoxime) methylsilane and bis (cyclohexylketoxime) methylsilane. However, the present invention is not limited to these. Of these, halogenated silanes and alkoxysilanes are particularly preferred.

Such a manufacturing method is described in, for example,
No.-69659, Japanese Patent Publication No. Hei 7-108928, Japanese Unexamined Patent Publication No. Sho 6
No. 3,254,149, JP-A-64-22904, and Japanese Patent Publication No. 2539445. Further, the isobutylene-based polymer having a reactive silicon group in the molecular chain is produced by adding a vinylsilane or an allylsilane having a reactive silicon group to a monomer mainly composed of isobutylene and copolymerizing the monomer.

Further, in the polymerization for producing an isobutylene-based polymer having a reactive silicon group at the terminal of the molecular chain, a vinylsilane or an allylsilane having a reactive silicon group other than the main component isobutylene monomer is copolymerized. After that, by introducing a reactive silicon group to the terminal, an isobutylene-based polymer having a reactive silicon group at the terminal and in the molecular chain is produced.

Examples of vinylsilanes and allylsilanes having a reactive silicon group include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, divinyldichlorosilane, divinyldimethoxysilane, allyltrichlorosilane, and allylsilane. Examples include methyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, diallyldichlorosilane, diallyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylmethyldimethoxysilane.

In the hydrogenated polybutadiene-based polymer, for example, first, a hydroxyl group of a terminal hydroxy-hydrogenated polybutadiene-based polymer is converted into an oxymetal group such as -ONa or -OK, and then a compound represented by the general formula (3): CH ₂ = ^{CH-R 3 -Y (3)} ( in the formula, Y is a chlorine atom, a halogen atom such as iodine atom, R ³ is -R ⁴ -, - R ⁴ -OCO- or -R ⁴ -CO
A divalent organic group represented by-(R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably an alkylene group, a cycloalkylene group, an arylene group, or an aralkylene group);
_{H 2 -, - R "-C} 6 H 5 -CH 2 - (R" carbon atoms 1 to 1
(Hydrocarbon group of 0) is particularly preferable) to produce a hydrogenated polybutadiene-based polymer having a terminal olefin group.

A method for converting a terminal hydroxyl group of a hydroxy-terminated hydrogenated polybutadiene polymer into an oxymetal group is as follows.
Alkali metals such as Na and K; metal hydrides such as NaH; metal alkoxides such as NaOCH ₃ ;
A method of reacting with an alkali hydroxide such as OH and KOH is exemplified. In the above-mentioned method, a terminal olefin hydrogenated polybutadiene polymer having almost the same molecular weight as the terminal hydroxy hydrogenated polybutadiene polymer used as a starting material can be obtained. Before reacting the organic halogen compound of the formula (3), a polyvalent organic halogen compound containing two or more halogens in one molecule such as methylene chloride, bis (chloromethyl) benzene, bis (chloromethyl) ether, etc. If the reaction is carried out, the molecular weight can be increased. Then, if the reaction is carried out with the organic halogen compound represented by the general formula (3), a hydrogenated polybutadiene polymer having a higher molecular weight and having an olefin group at the terminal can be obtained. Can be.

Specific examples of the organic halogen compound represented by the general formula (3) include, for example, allyl chloride,
Allyl bromide, vinyl (chloromethyl) benzene,
Allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy)
Examples include, but are not limited to, benzene and allyloxy (chloromethyl) benzene. Of these, allyl chloride is preferable because it is inexpensive and easily reacts.

The introduction of the reactive silicon group into the hydrogenated polybutadiene polymer at the terminal olefin is carried out by using a platinum catalyst as in the case of the isobutylene polymer having a reactive silicon group at the molecular chain end. It is produced by performing an addition reaction. The saturated hydrocarbon polymer having at least one reactive silicon group as the component (A) of the present invention has a cured product obtained by curing the polymer and having a 50% tensile stress value of ² to 6 kgf / cm ² . It is important that there be. Here, the 50% tensile stress of the cured product is as follows.

That is, at least one reactive silicon group
1 part of water, 3 parts of tin octylate, and 0.75 part of laurylamine were added to 100 parts of a saturated hydrocarbon polymer (parts by weight, hereinafter the same), and the mixture was thoroughly mixed and defoamed.
Pour into mm formwork. This is cured at 23 ° C. for 3 days and further at 50 ° C. for 4 days to obtain a cured product sheet having a thickness of about 3 mm. A No. 3 dumbbell in accordance with JIS-K6301 is punched from the sheet and a tensile test is performed (tensile speed: 500 mm / min). The tensile strength for 50% elongation at this time is defined as 50% tensile stress.

In the present invention, among the saturated hydrocarbon polymers having at least one reactive silicon group, the above 5
Only those having a value of 0% tensile stress of ² to 6 kgf / cm ² are used as the saturated hydrocarbon polymer (A). 50%
When the value of the tensile stress is less than 2 kgf / cm ² , the hardness may be insufficient, and when it exceeds 6 kgf / cm ² , the value of the maximum elongation may be small and the cured product may be brittle.

As described above, when the saturated hydrocarbon polymer having a reactive silicon group does not substantially contain an unsaturated bond which is not an aromatic ring in the molecule, an organic polymer having an unsaturated bond, Compared with a conventional sealing agent made of a rubber-based polymer such as an oxyalkylene-based polymer, the weather resistance is significantly improved. Further, since the polymer is a hydrocarbon polymer, it has good moisture barrier properties and water resistance, and has excellent adhesion performance to various inorganic base materials such as glass and aluminum, and has a low moisture barrier property. become. Further, in the present invention, the value of the 50% tensile stress is 2 to 6%.
Since a polymer of kgf / cm ² is used, the cured product has high modulus, high hardness and flexible rubber elasticity.

The content of the saturated hydrocarbon polymer having a reactive silicon group in the curable composition of the present invention is preferably 10% or more, more preferably 20% or more, and particularly preferably 30% or more. In the curable composition of the present invention, a photopolymerizable substance is used as the component (B) in order to further increase the hardness of the cured product and the weather resistance. The photopolymerizable substance is a compound having an unsaturated group that causes a polymerization reaction when a double bond in a molecule is activated by irradiation with light. Various substances such as organic monomers, oligomers, resins and compositions containing these are known as this kind of substance, and any commercially available substance can be used in the present invention. When a photopolymerizable substance is added as the component (B) to the component (A), the component (B) can form a hard film on an adhesive surface with an adherend such as glass by light irradiation. It is considered that the component (A) acts as a weather resistance improving agent. However, the initial adhesive strength does not decrease.

The photosensitive group (unsaturated group) of the photopolymerizable substance
In the case of monofunctionality having only one, only a linear polymer is formed by photopolymerization. However, in the case of a polyfunctional photopolymerizable substance having two or more photosensitive groups (unsaturated groups), since photopolymerization and photocrosslinking occur simultaneously,
Since a polymer molecule having a network structure can be formed and a hard film can be formed by an adhesive interface, weather resistance and mechanical properties (hardness) are improved. The effect of improving weather resistance and mechanical properties increases as the number of photosensitive groups (unsaturated groups) in the photopolymerizable substance increases. To remarkably improve these properties, the number of functional groups must be 4 or more. Preferably, 5 or more are more preferable.

Representative examples of the photopolymerizable unsaturated group contained in the photopolymerizable substance include a vinyl group, an allyl group, a vinyl ether group, a vinyl thioether group, a vinyl amino group,
Examples thereof include an acetylenically unsaturated group, an acryloyl group, a methacryloyl group, a styryl group and a cinnamoyl group. Of these, (meth) acrylates having a acryloyl group or a methacryloyl group as a photosensitive group are available with high photoinitiating efficiency It is more preferable because it is easy to perform. In this specification, (meth) acrylate is a general term for acrylate and methacrylate.

The (meth) acrylate having 4 or more functional groups is a monomer, an oligomer or a mixture thereof having 4 or more acrylic or methacrylic unsaturated groups. Specific examples of the monomer include: Examples thereof include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta, and hexa (meth) acrylate. Further, specific examples of the oligomer include oligoesters having a molecular weight of 10,000 or less, such as polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate.

When the photopolymerizable substance having four or more functional groups is used in the composition of the present invention, the curable composition contains a saturated hydrocarbon polymer having a reactive silicon group. The cured material properties such as hardness and weather resistance can be improved. The compounding amount of the photopolymerizable substance is preferably from 0.1 to 20 parts, more preferably from 1 to 10 parts, particularly preferably from 2 to 5 parts, per 100 parts of the component (A). If the compounding amount is less than 0.1 part, the effect of improving the properties of the cured product such as hardness and the weather resistance may not be sufficient, and if it exceeds 20 parts, the storage stability of the curable composition decreases. Sometimes.

Various additives are added to the curable composition of the present invention as needed. Examples of such additives include, for example, a curing catalyst that promotes a silanol condensation reaction, a physical property modifier that adjusts the tensile properties of the resulting cured product,
Plasticizers, fillers, adhesion improvers, antioxidants, radical inhibitors, ultraviolet absorbers, metal deactivators, ozone deterioration inhibitors, light stabilizers, phosphorus peroxide decomposers, lubricants, pigments,
Foaming agents and the like.

Specific examples of such additives include, for example,
Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-1088928,
JP-A-63-254149, JP-A-64-22904
It is described in each specification of the issue. When the curable composition of the present invention is used for various glasses such as general-purpose inorganic glass (float glass), it exhibits a remarkable effect of improving weather resistance and adhesion, but when used as a sealing material composition for heat ray reflective glass, The effect of improving the weather resistance is particularly remarkable.

The heat ray reflective glass has an optical function such as reflecting or absorbing light of a specific wavelength by coating the glass surface with a metal film, a metal nitride film, a metal oxide film, or the like. Shows glass. The effect of the photopolymerizable substance of the present invention is similarly observed when the above-mentioned various additives are added. That is, when the curable composition of the present invention is used for a sealing material for a double glazing or a sealing material for an SSG method, and a sealing material for direct glazing such as an automobile, by adding this photopolymerizable substance,
The mechanical properties (hardness, etc.) and weather resistance of these sealants can be improved.

[0044]

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

[0045]

[Production Example 1] A three-way cock was attached to a 500 ml pressure-resistant glass container, and the inside of the container was replaced with nitrogen. Thereafter, the container was dried by leaving it over one night with ethylcyclohexane (with molecular sieves 3A) using a syringe. 54 ml) and 126 ml of toluene (dried by leaving it together with Molecular Sieves 3A for one night or more), 0.7 ml of p-DCC (the following compound)
6 g (3.28 mmol) were added.

[0046]

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Next, a liquefied gas sampling tube made of pressure-resistant glass with a needle valve containing 56 ml of isobutylene monomer was connected to a three-way cock, and the polymerization vessel was cooled by placing it in a -70 ° C. dry ice / ethanol bath. The inside of the container was evacuated using a vacuum pump. After opening the needle valve and introducing the isobutylene monomer from the liquefied gas collecting tube into the polymerization vessel, the inside of the vessel was returned to normal pressure by introducing nitrogen from one of the three-way cocks. Next, 0.112 g (1.2 mmol) of 2-methylpyridine was added. Next, 1.65 ml of titanium tetrachloride (15.1 mmol)
l) In addition, polymerization was started. After a reaction time of 70 minutes, 0.89 g (7.9 mmol) of allyltrimethylsilane was added to carry out an allyl group introduction reaction at the polymer terminal. After a reaction time of 120 minutes, the reaction solution was washed four times with 200 ml of water, and then the solvent was distilled off to obtain an allyl-terminated isobutylene polymer.

Next, 40 g of the allyl-terminated isobutylene polymer thus obtained was dissolved in 20 ml of n-heptane, heated to about 70 ° C., and then methyldimethoxysilane 1.5 [eq / vinyl group], platinum (vinyl) Siloxane)
Complex 1 × 10 ⁻⁴ [eq / vinyl group] was added, and a hydrosilylation reaction was performed. Follow the reaction by FT-IR,
The olefin absorption at 1640 cm ^-1 disappeared in about 4 hours.

The reaction solution was concentrated under reduced pressure to obtain a desired isobutylene polymer having reactive silicon groups at both ends. (The following compounds)

[0050]

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The yield was calculated from the yield of the polymer thus obtained, and the Mn and Mw / Mn were determined by the GPC method, and the terminal structure was determined by 300 MHz ¹ H-NMR analysis. Proton: 6.5 to 7.5 ppm, methyl proton bonded to a silicon atom derived from a polymer end: 0.0 to 0.1 ppm
And methoxy protons: 3.4 to 3.5) were obtained by measuring and comparing the intensity of the resonance signals. ¹ H-NMR
Is a Varian Gemini 300 (300 MHz
for ¹ H) in CDCl ₃ .

The FT-IR is IR-4 manufactured by Shimadzu Corporation.
08, GPC is Waters LC
Module 1, column is Shodex K-804
This was performed using Molecular weights are given as relative molecular weights to polystyrene standards. The analytical value of the polymer is
Mn = 17500, Mw / Mn = 1.14, Fn (silyl) = 1.91. (The number average molecular weight is in terms of polystyrene, the number of terminal silyl functional groups is isobutylene polymer 1
Number per molecule).

[0053]

Production Example 2 1.16 g of p-DCC (5.02
mmol), 0.093 g of 2-methylpyridine (1.0
mmol), 1.22 g of allyltrimethylsilane (1
An isobutylene-based polymer having a reactive silicon group was synthesized in the same manner as in Production Example 1 except that the amount was changed to 0.8 mmol).

The analysis value of the polymer was as follows: Mn = 11400,
Mw / Mn = 1.23 and Fn (silyl) = 1.76.

[0055]

Example 1 and Comparative Example 1 From the analytical values of the base polymers synthesized in Production Examples 1 and 2, the number average molecular weight per reactive silicon group, that is, the number average molecular weight (Mn) was obtained.
And the ratio (Mn) of the number of reactive silicon groups per molecule (Fn)
n / Fn) was calculated. Table 1 shows the values of Mn / Fn.

Next, the 50% tensile stress of the cured product of the base polymer synthesized in Production Examples 1 and 2 was measured. Table 1 shows the results. The 50% tensile stress is measured by the following method as described above. That is, 1 part of water, 3 parts of tin octylate, and 0.75 part of laurylamine are added to 100 parts of the base polymer, mixed well, defoamed, and then poured into a 3 mm-thick mold. Put this at 23 ° C for 3 days
After curing at 50 ° C. for 4 days, a cured product sheet having a thickness of about 3 mm is obtained. A No. 3 dumbbell compliant with JIS-K6301 was punched out of this sheet, and a tensile test was performed (tensile speed: 500 mm / min). The tensile strength for 50% elongation at this time was defined as 50% tensile stress.

Polymer 100 obtained in Production Example 1 or 2
For the part, a paraffin-based process oil (manufactured by Idemitsu Kosan Co., Ltd., trade name: Diana Process PS-32) 90
Part, heavy calcium carbonate (Maruo Calcium Co., Ltd., trade name Snow Light SS) 30 parts, colloidal calcium carbonate (Shiraishi Industry Co., Ltd., trade name EDS-D10A) 100
Section, talc (trade name: talc L, manufactured by Fuji Talc Kogyo Co., Ltd.)
MR) 100 parts, Na ₂ SO ₄ .10H ₂ O 6 parts, γ-glycidoxypropyltrimethoxysilane (Nippon Unicar Co., Ltd., trade name: silane coupling agent A-187) 2
Parts, 4 parts of γ-isocyanatopropyltriethoxysilane (manufactured by Nippon Unicar Co., Ltd., trade name: silane coupling agent Y-9030), a photopolymerizable substance (Toagosei Co., Ltd.)
(Trade name) Aronix M400 (dipentaerythritol penta and hexaacrylate) was added, and the mixture was kneaded well with a three-paint roll to obtain a main ingredient.

A curing catalyst (Nitto Kasei Co., Ltd.)
(Trade name: U-220) was weighed at a weight ratio of 110: 1, kneaded sufficiently, filled in a mold on which a Teflon sheet was laid, and subjected to standard curing (23 ° C. × 7 days + 50 ° C. × 7 days). The value of the hardness of the cured product was measured using a rectangular parallelepiped sample having a size of 12 × 12 × 50 mm obtained later. The hardness of this rod-shaped cured product was measured using a Shimadzu Rubber Hardness Tester Model 200 manufactured by Shimadzu Corporation in accordance with a spring type hardness test A type defined in JIS K 6301-1975. The measurement was performed at 5 points.
The average was displayed. Table 1 shows the results.

[0059]

[Table 1]

As shown in Table 1, the base polymer of Production Example 1 having a large value of Mn (number average molecular weight) and Mn / Fn (number average molecular weight per reactive silicon group) and a small value of 50% tensile stress was used. In this case, the hardness of the cured product of the blended composition was small, so that it was not suitable as a base polymer for a sealing material for high modulus and high hardness. On the other hand, the value of 50% tensile stress is 2 to 6 kgf / cm
^In the case of using the base polymer of Production Example ² which is 2,
It can be seen that the hardness value is large and suitable as a base polymer for a sealing material for high modulus and high hardness.

[0061]

Examples 2 to 4 and Comparative Examples 2 to 4 100 parts of the polymer obtained in Production Example 2 having a 50% tensile stress value of ² to 6 kgf / cm 2 was added to a paraffin-based process oil (Idemitsu Kosan (Idemitsu Kosan) Diana Process PS-3
2) 90 parts, heavy calcium carbonate (manufactured by Maruo Calcium Co., Ltd., trade name Snow Light SS) 30 parts, colloidal calcium carbonate (manufactured by Shiraishi Industry Co., Ltd., trade name EDS-D10)
A) 100 parts, talc (manufactured by Fuji Talc Kogyo KK, trade name: talc LMR) 100 parts, Na ₂ SO ₄ .10H ₂ O 6
Parts, light stabilizer nickel dimethyldithiocarbamate (manufactured by Sanshin Chemical Co., Ltd., trade name: Sandant NBC) 3 parts,
[2,2′-thiobis (4-t-octylphenolate)]-n-butylamine nickel (manufactured by ACC Corporation)
3 parts of brand name CIASORB UV-1084), antioxidant (manufactured by Ciba Geigy Co., Ltd., trade name of Irganox 1)
010) 1 part, an ultraviolet absorber (manufactured by Ciba Geigy Co., Ltd.)
1 part of trade name Tinuvin 327), light stabilizer (Sankyo Co., Ltd.)
Manufactured by Sanol LS-770), 1 part, γ-glycidoxypropyltrimethoxysilane (Nihon Unicar Co., Ltd.)
Silane coupling agent A-187), 2 parts, γ
-Isocyanatepropyltriethoxysilane (trade name, silane coupling agent Y-90, manufactured by Nippon Unicar Co., Ltd.)
30) 4 parts, as a photopolymerizable substance, tripropylene glycol glycol diacrylate (manufactured by Toagosei Co., Ltd.
Trade name Alonix M220), trimethylolpropane triacrylate (trade name, Alonix M309, manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (trade name, manufactured by Toagosei Co., Ltd., trade name Aronix M45
0) or dipentaerythritol penta and hexaacrylate (trade name: Aronix M400, manufactured by Toagosei Co., Ltd.) were added in the number shown in Table 2, and kneaded well with a three paint roll to obtain a base material.

Further, a paraffin-based process oil (manufactured by Idemitsu Kosan Co., Ltd., trade name: Diana Process PS-32) 1
0 parts, heavy calcium carbonate (manufactured by Maruo Calcium Co., Ltd.
Disposer: 20 parts of snow light SS (trade name), 4 parts of curing catalyst (trade name: U-220, manufactured by Nitto Kasei Co., Ltd.), and 2.5 parts of carbon black (CB # 30, manufactured by Mitsubishi Chemical Corporation) After manually kneading and kneading in a Le Cup, the operation of stirring the mixture at 10,000 rpm for 10 minutes using an Excel Auto Homogenizer manufactured by Nippon Seiki Seisaku-sho, Ltd. was performed three times to adjust the curing agent.

After weighing the above base material and curing agent in a weight ratio of 12: 1 and kneading them sufficiently, filling them in a mold covered with a Teflon sheet, standard curing (23 ° C. × 7 days + 50 ° C. × 7 days) The value of the hardness of the cured product was measured using a rectangular parallelepiped sample having a size of 12 × 12 × 50 mm obtained after the above. The hardness of this rod-shaped cured product was measured using a Shimadzu Rubber Hardness Tester Model 200 manufactured by Shimadzu Corporation in accordance with a spring type hardness test A type defined in JIS K 6301-1975. The measurement was performed at five points, and the average value was displayed. Table 2 shows the results.

[0064]

[Table 2]

As shown in Table 2, it can be confirmed that the value of the hardness of the cured product can be improved by adding a photopolymerizable substance having four or more functional groups in one molecule.

[0066]

Examples 5 to 8 and Comparative Examples 5 to 7 The above-mentioned main agent and curing agent were weighed at a weight ratio of 12: 1 and thoroughly kneaded.
According to the method for preparing a tensile adhesion test specimen specified in SA5758-1992, a glass substrate assembled into an H-shape was filled with a foam in the composition while squeezing with a spatula, and cured in an oven. Curing conditions are 23 ° C x 7 days + 5
0 ° C. × 7 days. The substrate used for the H-type tensile test was J
Float glass conforming to IS A 5758-1992 (manufactured by Koensha: Designated by the Japan Sealing Material Manufacturers Association, dimensions: 3
× 5 × 0.5 cm), a heat-reflective glass coated on the surface with TiOx by sputtering (Central Glass Co., Ltd., trade name: SGY-32, dimensions: 5 × 5 ×
0.6 cm) and a heat-reflective glass (manufactured by Central Glass Co., Ltd., trade name: KLS, dimensions: 5 × 5 × 0.6 cm) having TiOx fused to the surface. These adherends
Before filling the composition, it was washed with methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd .: special grade) and wiped with a clean cotton cloth.

The cured product for the H-type tensile test produced by the above method was subjected to a tensile adhesion test after the weather resistance test, and the weather resistance adhesion was evaluated by comparing the tensile characteristics and the fracture mode. The tensile adhesion test was conducted according to JIS A 5758-199.
According to 2 prescribed tensile adhesion test method, in a constant temperature room at a temperature of 23 ° C. and a humidity of 50 ± 10%, a tensile speed of 50 mm / min.
Under the conditions described above using Shimadzu Autograph AG-2000A. Cohesive failure (CF) / thin layer fracture (TC) in Table 1
F) The ratio of interfacial fracture (AF) is a ratio determined by visually observing the fracture surface after the tensile test. The weather resistance test used sunshine carbon as the light source and the black panel temperature was 6
Sunshine Super Long Life Weather Meter WEL-SUN manufactured by Suga Test Instruments Co., Ltd. set at 3 ° C
-A sample for an H-type tensile test was put in HC, and after being exposed in a weather resistance tester (SWOM) for the time shown in Table 3, the sample was taken out and subjected to an H-type tensile adhesion test. Table 3 shows the results.

For reference, Table 4 shows the results of a tensile adhesion test performed before the weather resistance test using the H-type tensile test cured product prepared by the above method.

[0069]

[Table 3]

[0070]

[Table 4]

As shown in Table 3, when no photopolymerizable substance was added (Comparative Examples 5 to 7), when float glass, which is a common glass, was used as an adherend, 100% even after exposure to SWOM for 3000 hours. Although cohesive failure is shown, when heat ray reflective glass (SGY-32, KLS) is used as the adherend, the fracture mode after SWOM exposure increases the rate of interfacial failure, and provides sufficient weather resistance for various glasses. It turns out that it does not have adhesiveness. However, when 3 parts or 6 parts of the photopolymerizable substance was added (Examples 5 to 8), the weather resistance to various glasses was good, and the rate of cohesive failure was high regardless of which glass was used. Recognize. Also, 5
As can be seen from the comparison of the values of 0% tensile stress, maximum tensile stress, and elongation at maximum load, the addition of the photopolymerizable substance does not adversely affect the properties of the cured product. Thus, the weathering adhesion of the sealing material composition comprising the saturated hydrocarbon polymer having at least one reactive silicon group in the molecule to the heat ray reflective glass is improved by the addition of the photopolymerizable substance. Can be confirmed.

As described above, a cured product comprising a saturated hydrocarbon polymer having at least one reactive silicon group in the molecule and having a 50% tensile stress value of ² to 6 kgf / cm ² of the cured product. It can be confirmed that the weather resistance and the hardness of the cured product of the hydrophilic composition to the glass substrate can be improved by adding a photopolymerizable substance having 4 or more functional groups in one molecule that can be polymerized by irradiation with light. .

[0073]

The curable composition of the present invention has weather resistance to various glass substrates, especially heat ray reflective glass, and
The hardness of the cured product can be significantly improved. Further, the curable composition of the present invention can be used as a sealing material for double-glazing or SS.
Used in areas where light enters the bonding surface, such as sealing materials for the G method, and is particularly useful as an elastic sealant that requires high modulus and high hardness. Can be held over.

Claims (10)

[Claims] (A) The value of the 50% tensile stress of the cured product is (A)
2-6kgf / cm ^TwoIs water bound to a silicon atom
Having an acid group or a hydrolyzable group, forming a siloxane bond
At least one silicon-containing group that can be crosslinked by
And (B) irradiation with light
Having 4 or more functional groups in one molecule
Curable composition characterized by containing a curable substance. 2. A silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond is represented by the general formula (1): (Wherein, R ¹ and R ² each independently represent a carbon number of 1 to
20 alkyl groups, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms or (R ′) ₃ SiO—
(R ′ is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms). X is each independently a hydroxyl group or a hydrolyzable group. Further, a is 0, 1,
B is 0, 1, or 2, and a and b do not become 0 at the same time. Also, m
Is a group represented by the formula (1): 0 or an integer of 1 to 19). 3. The curable composition according to claim 2, wherein X is an alkoxy group. 4. The saturated hydrocarbon polymer has a number average molecular weight of 7000 to 15,000.
The curable composition according to the above. 5. A compound having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a number average molecular weight of 400 per silicon-containing group which can be crosslinked by forming a siloxane bond.
The curable composition according to claim 1, wherein the number is from 0 to 7000. 6. The curable composition according to claim 1, wherein the saturated hydrocarbon-based polymer is a polymer having a total amount of repeating units derived from isobutylene of 50% by weight or more. 7. The curable composition according to claim 1, wherein the photopolymerizable substance is an acrylate or a methacrylate. 8. An amount of 100 parts by weight of the component (A)
The curable composition according to claim 1, wherein the curable composition contains 0.1 to 20 parts by weight of the component (B). 9. A sealing material composition for a double glazing comprising the curable composition according to claim 1. Description: 10. A sealing material composition for heat ray reflective glass, comprising the curable composition according to claim 1. Description: