JP2001288366A - Hot-melt composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hot-melt composition whose characteristics are scarcely deteriorated at high temperature and can easily be produced. SOLUTION: A hot-melt composition characterized by comprising (A) an organic polymer cured product in which at least one of substantially cross-linked points is a siloxane bond and (B) a component selected from a hot-melt resin, a thermoplastic resin and a plasticizer. Thus, the hot-melt composition which can easily be produced and whose physical characteristics are scarcely deteriorated at high temperature is obtained, and the composition is used to obtain adhesive materials having good characteristics and rubbery spacers which have good characteristics and are used for multiple glazing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a hot melt composition containing an organic polymer cured product in which at least a part of substantial crosslinking points is a siloxane bond.

[0002]

2. Description of the Related Art Hot-melt compositions have the characteristics of flowing at high temperatures and solidifying or becoming highly viscous upon cooling. Therefore, they are excellent in workability and are used in various applications such as adhesives, sealants and gaskets. It is used. In the production of multilayer glass, a rubber-like spacer using a hot melt composition simplifies the production process and contributes to the spread of multilayer glass. In addition, it is widely used for waterproofing seals for automobiles, waterproofing tapes for construction and electrical insulating tapes.

[0003] A material using a hot melt composition has the above-mentioned good characteristics, but generally has problems such as deterioration of strength characteristics and generation of creep at a high temperature. Although butyl rubber, polyisobutylene, and the like are used as the hot melt resin, some studies have been made so far to improve long-term durability and reliability.

JP-A-53-20501 discloses that the gelation ratio is 3
A solution has been achieved by using a partially vulcanized butyl rubber having a partial vulcanization degree of 0 to 50%. However, due to the characteristics of the production method, partially vulcanized butyl rubber has a high risk of its physical properties fluctuating and has a high viscosity even at high temperatures. .

Further, Japanese Patent Application Laid-Open No. Hei 4-15937 proposes a solution to the problem by using a polymer having a reactive silicon group in combination with a hot melt resin. JP-A-11-2
In 17243 and WO97474878, a compound is proposed in which a desiccant substance is further added to a polymer having a reactive silicon group and a hot melt resin, and a siloxane bond is formed as a result of a curing reaction after discharge of the hot melt. Accordingly, application to rubber-like spacers for double-glazing is disclosed. The polymer having a reactive silicon group is suitable for the application because it has excellent weather resistance and low moisture permeability, but since the curing reaction proceeds with moisture, it is difficult to adjust the curing speed, and the curing is performed quickly. Therefore, in addition to the conventional hot melt application equipment, it is necessary to improve equipment such as mixing of two liquids. In particular, in a composition to which a desiccant or a moisture absorbing component is added, the moisture required for curing is required. There is a problem that the range of selection of the composition such as the balance between the composition and the amount of the desiccant is greatly restricted.

[0006]

SUMMARY OF THE INVENTION A hot melt composition which is less likely to deteriorate at high temperatures and is easy to produce is obtained.

[0007]

Means for Solving the Problems The present inventors have developed a hot melt composition characterized by containing an organic polymer cured product (A) in which at least a part of substantial crosslinking points is a siloxane bond. It has been found that by using the composition, the production is easy and the property deterioration at high temperatures is small.

Further, the above-mentioned hot melt composition comprises:
(B) As a component, a hot melt resin, a thermoplastic resin,
It has been found that when one or more components selected from plasticizers are contained, they have good properties.

Furthermore, it has been found that by using the above-mentioned hot melt composition, an adhesive material having good properties and a rubber spacer for a double-layer glass can be obtained.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The organic polymer cured product of the present invention, in which at least a part of the substantial crosslinking points as the component (A) is a siloxane bond, is not particularly limited as long as the above conditions are satisfied. The main chain skeleton can be selected from, for example, saturated hydrocarbons, polyethers, polyesters, acrylics, and the like. Saturated hydrocarbons are desirable from the viewpoint of high-temperature stability as a hot melt composition.

In the present invention, the organic polymer cured product in which at least a part of a substantial crosslinking point has a siloxane bond is a crosslinked product obtained by bonding a plurality of organic polymers to a portion having a siloxane bond. Preferably, it is formed. That is, it is preferable that the crosslinked product having a network structure (network) has a siloxane bond at a knot portion of the network. In addition, the cured organic polymer of the present invention generally refers to an organic polymer having a crosslinkable functional group, which has been crosslinked by a chemical reaction.

In the present invention, the content of the cured organic polymer in the hot melt composition containing the cured organic polymer as the component (A) is not limited as long as physical properties and fluidity are compatible. Of the fluid components in the hot melt composition, 5 to 80% by weight is preferable, and 5 to 50% by weight is more preferable.

If the amount is less than 5% by weight, the effect of improving the high-temperature properties may not be sufficient, and if it exceeds 80% by weight, the fluidity may be low and the construction may be difficult.

Good properties are exhibited when the hot melt composition of the present invention contains, as the component (B), a component selected from a hot melt resin, a thermoplastic resin and a plasticizer. The hot melt resin as the component (B) is not limited as long as it meets the purpose of the present invention, and includes, for example, butyl rubber, partially crosslinked butyl, polyisobutylene, styrene block polymer, EVA, olefin, polyester, and polyamide. And a reactive urethane hot melt resin. The thermoplastic resin as the component (B) is not limited as long as it meets the purpose of the present invention, and examples thereof include a polyolefin resin, a polystyrene resin, a vinyl chloride resin, an acrylic resin, and a fluororesin. The plasticizer of the component (B) is not limited as long as it complies with the object of the present invention. Examples of the plasticizer include polyvinyl-based oligomers such as polybutene, hydrogenated polybutene, hydrogenated α-olefin oligomer and atactic polypropylene; biphenyl, triphenyl and the like. Aromatic oligomers such as hydrogenated polybutadiene; paraffinic oligomers such as paraffin oil and chlorinated paraffin oil; cycloparaffinic oligomers such as naphthenic oil; dibutyl phthalate, diheptyl phthalate, di (2 Phthalic acid esters such as -ethylhexyl) phthalate, butylbenzyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate and diundecyl phthalate; di (2-ethylhexyl) adipate, di-n-octyl Non-aromatic dibasic acid esters such as ruadipate, diisononyl adipate, diisodecyl adipate, di (2-ethylhexyl) sebacate and di-2-ethylhexyl tetrahydrophthalate; aromatics such as tri-2-ethylhexyl trimellitate and triisodecyl trimellitate Fatty acid esters such as butyl oleate, methyl acetyl ricinoleate and pentaerythritol ester; esters of polyalkylene glycol such as diethylene glycol benzoate and triethylene glycol dibenzoate; phosphoric acid such as tricresyl phosphate and tributyl phosphate Esters: Epoxy plasticizers such as epoxidized soybean oil and epoxidized linseed oil. These may be used alone or in combination of two or more.

In the present invention, the content of the cured organic polymer as the component (B) in the hot melt composition is not limited as long as it is compatible with physical properties and fluidity. Of the fluid components, 5 to 80% by weight is preferable, and 5 to 50% by weight is more preferable.

The component (B) has a structure, a composition, an added amount,
The combination or the like affects the properties of the hot melt composition such as physical properties at normal temperature and fluidity at high temperature.

Each component of the component (B) can be used alone or in combination. For example, in the case of a hot melt composition which is required to have water stopping properties, low gas permeability and weather resistance, as a component (A), a cured saturated hydrocarbon polymer, and among components (B), a hot melt resin, Hot melt compositions containing butyl rubber, polyisobutylene, and polybutene and process oil as a plasticizer are effective. When the hot melt composition further contains polyethylene as a thermoplastic resin as the component (B), it is possible to obtain a hot melt composition having an improved elastic modulus at low temperature in addition to the above characteristics. it can.

The hot melt composition of the present invention further comprises a desiccant substance or a hygroscopic substance as the component (C) in addition to the component (A) and the component (B). It is particularly effective as a rubber spacer for double-glazing because it has a good workability, which is a characteristic, and forms a molded article exhibiting moisture absorption after construction. As the component (C), a desiccant substance or a hygroscopic substance is dispersed and mixed uniformly or with a certain distribution.
As the desiccant substance or the hygroscopic substance, those that function to adsorb moisture even in the base rubber are used,
For example, powdery synthetic crystalline zeolite, synthetic crystalline metal aluminosilicate, activated alumina, sintered silica,
Anhydrous calcium sulfate, silica gel and the like can be used. Among them, molecular sieves 3A, 4A, 9F and the like are most suitable.

The compounding amount of the desiccant or hygroscopic substance (C) is not particularly limited as long as the fluidity and hygroscopicity of the hot melt composition are exhibited. 40% by weight is preferred, and 10 to 30% by weight
Is more preferred.

The method for producing the cured organic polymer as the component (A) of the present invention is not particularly limited as long as at least a part of the substantial crosslinking points is a siloxane bond.
A method of reacting and curing an organic polymer having a hydroxyl group or a hydrolyzable silicon-containing group to form a siloxane bond, a method of polymerizing and curing an organic monomer containing an organic monomer having a siloxane bond, Method of reacting and curing a compound having both a bond and a hydrosilyl group and an organic polymer having a substituent capable of being bonded to a hydrosilyl group, and curing an organic polymer having a siloxane bond by using a rearrangement reaction of the siloxane bond Although there are methods, etc., at least one silicon-containing group which has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be cross-linked by forming a siloxane bond, due to availability of raw materials and ease of curing reaction. A method of curing the organic polymer (a) is desirable.

The method for producing the hot melt composition containing the components (A) and (B) is not particularly limited, and a composition containing the component (A) is prepared and the component (B) is contained. A method of mixing the composition, a method of synthesizing a cured organic polymer as the component (A) in the composition containing the component (A) and the component (B), and a method of synthesizing the composition containing the component (B). Examples of the method include a method of mixing a composition obtained by synthesizing a cured organic polymer as the component (A) with a composition containing the component (B). In either method,
It is important to select the composition, temperature, curing rate, mechanical performance, etc. so as to satisfy the production conditions such as mixing and kneading operations. For example, the reactive silicon group-containing organic polymer as the component (a) is A composition obtained by curing a siloxane bond-containing organic polymer as the component (A) by curing at room temperature in a plasticizer as the component (B) to obtain a hot melt resin and a thermoplastic resin as the component (B) Can be easily produced by kneading the composition containing the compound with a kneading device at a high temperature. In addition to the components described above, necessary additives such as an antioxidant, an adhesion-imparting agent, a filler, a surfactant and the like can be freely added to each composition under conditions that can be produced.

The main component of the organic polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom, which is a component (a) of the present invention, and having at least one silicon-containing group capable of crosslinking by forming a siloxane bond. As a chain skeleton,
According to the characteristics of the component (A), for example, a saturated hydrocarbon,
It can be selected from polyether, polyester, acryl and the like, but from the viewpoint of high temperature stability as a hot melt composition, a saturated hydrocarbon is desirable.

The saturated hydrocarbon polymer having a reactive silicon group which can be used for the component (a) of the present invention is a polymer substantially containing no carbon-carbon unsaturated bond other than the aromatic ring. Examples thereof include polyethylene, polypropylene, polyisobutylene, hydrogenated polybutadiene, and hydrogenated polyisoprene.

The reactive silicon group is represented by the general formula (1):

[0026]

Embedded image (Wherein R ¹ and R ² are each independently a hydrogen atom,
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
A triorganosiloxy group represented by SiO- (R ', each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms). Also,
X is each independently a hydroxyl group or a hydrolyzable group. Further, a is any of 0, 1, 2, 3, and b
Is 0, 1, or 2, and a and b do not become 0 at the same time. And m is 0 or an integer of 1 to 19).

Examples of the hydrolyzable group include commonly used groups 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 silicon atom forming the reactive silicon group is 1
The number is preferably at least 20, but in the case of silicon atoms linked by a siloxane bond or the like, the number is preferably at most 20.

In particular, the general formula (2)

[0032]

Embedded image (Wherein, R ² , X and a are the same as those described above) are preferred because the raw material can be easily obtained.

The number of reactive silicon groups in one molecule of the saturated hydrocarbon polymer is one or more on average, 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 present at the terminal or inside the molecular chain of the saturated hydrocarbon polymer, or may be present 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 (1) an olefin having 1 to 6 carbon atoms such as ethylene, propylene, 1-butene and isobutylene. Polymerization using a compound as a main monomer, (2) homopolymerization of a diene-based compound such as butadiene, isoprene, or copolymerization with the olefin-based compound, followed by hydrogenation. However, an isobutylene-based polymer or a hydrogenated polybutadiene-based polymer is preferable because a functional group can be easily introduced into a terminal, a 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 a copolymer 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. Examples of such a copolymer component include 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, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinyl Methylsilane, tetravinylsilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallylmethoxymethoxy, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ
-Methacryloyloxypropylmethyldimethoxysilane.

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 case of the hydrogenated polybutadiene-based polymer and other saturated hydrocarbon-based polymers, similarly to the case of the above-mentioned isobutylene-based polymer, other monomer units besides the main monomer unit are used. May be contained.

The saturated hydrocarbon polymer having a reactive silicon group used in the present invention includes a post-polymerization double bond 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 preferably about 500 to 50,000, particularly preferably about 1,000 to 20,000. Liquid or fluid materials are preferred from the viewpoint of easy handling.

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, the isobutylene-based polymers having a reactive silicon group at the end of the molecular chain can be obtained by a polymerization method called an inifer method (initiator and chain transfer agent which are both used as an inifer). End-functional type, preferably an all-terminal-functional isobutylene-based polymer obtained by a cationic polymerization method using a specific compound. 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

[0045]

Embedded image (Wherein R ¹ , R ² , X, a and b are the same as described above) (this compound is a compound in which a hydrogen atom is bonded to a group represented by the general formula (1)) And preferably a general formula

[0046]

Embedded image (Wherein, R ² , X and a are the same as described above) to introduce a reactive silicon group into the polymer by subjecting the hydrosilane compound represented by the formula (1) to an addition reaction called hydrosilylation reaction using a platinum catalyst. There is a way to do it. 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,
-69659, JP-B-7-108928, JP-A-251468, JP-A-64-22904, and JP-A-2539445.

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 containing isobutylene as a main component and copolymerizing the monomer. Is done.

Further, during 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 hydroxy-terminated 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), thereby reacting an organic halogen compound represented by the formula (1) to obtain a hydrogenated polybutadiene polymer having a terminal olefin group (hereinafter referred to as a hydrogenated polybutadiene polymer having a terminal olefin). Is also manufactured).

A method for converting a terminal hydroxyl group of a terminally 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 hydrogenated polybutadiene-terminated olefin polymer having substantially the same molecular weight as that of the hydroxy-terminated polybutadiene-based polymer used as the starting material can be obtained. Is a polyvalent organic compound containing two or more halogens in one molecule, such as methylene chloride, bis (chloromethyl) benzene and bis (chloromethyl) ether, before reacting the organic halogen compound of the general formula (3). The molecular weight can be increased by reacting with a halogen compound, and then by reacting with an 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.

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 a reactive silicon group into the hydrogenated polybutadiene-based polymer at the terminal olefin is carried out by using a platinum-based catalyst as in the case of an isobutylene-based polymer having a reactive silicon group at the molecular chain end. It is produced by performing an addition reaction.

As a method for curing the reactive silicon-based organic polymer as the component (a) to obtain a cured product as the component (A), a reactive silicic acid group in the component (a) in the presence of a silanol condensation catalyst is used. And a method of reacting water with a hydroxyl group-containing compound such as water or silanol to form a siloxane bond.

Examples of the silanol condensation catalyst include acids, base catalysts, divalent and tetravalent tin-based curing catalysts, titanium-based curing catalysts, aluminum-based curing catalysts, and amine-based curing catalysts.

Specific examples of the tetravalent tin-based curing catalyst include, for example, tetravalent tin carboxylate salts such as dibutyltin bisacetylacetonate, dibutyltin dialkoxide, dibutyltin dilaurate, dibutyltin maleate and dibutyltin diacetate. can give. Specific examples of the silanol condensation catalyst other than the above-mentioned tetravalent tin curing catalyst include tin octylate and the like.
Divalent tin-based curing catalyst; titanates such as tetrabutyl titanate and tetrapropyl titanate; aluminum-based curing catalysts such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetyl Acetonate; lead octylate; butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, 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)
Amine curing catalyst such as undecene-7 (DBU); low molecular weight polyamide resin obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; γ-aminopropyltrimethoxysilane; −
A known silanol condensation catalyst such as a silane coupling agent having an amino group such as (β-aminoethyl) aminopropylmethyldimethoxysilane;

These catalysts may be used alone,
Two or more kinds may be used in combination.

The hot melt composition of the present invention contains, in addition to the components (A) to (C) described above, a tackifier, a filler, a flexibility control agent, an antioxidant, and a silane coupling agent. , A physical property adjuster for adjusting the tensile properties of the resulting cured product, a photocurable resin, an anti-sagging agent, a solvent, a flame retardant, a lubricant, a pigment, a spacer shape retainer, a flow improver, etc. Various additives are added. In addition, a reactive silicon group-containing organic polymer can be added for the purpose of improving properties.

These additional components are manufacturable and
It is possible to add at any stage of the production process as long as the physical properties can be expressed, for example, a method used together with the production of the component (A), or after mixing the components (A) and (B). Etc. are exemplified.

Examples of the tackifier include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, hydrogenated alicyclic hydrocarbon resins, alicyclic hydrocarbon resins, cumarone resins, terpene resins, Rosin derivatives and the like can be mentioned.

Examples of the filler include wood powder, parve, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice hull powder, graphite, diatomaceous earth, clay, fumed silica and precipitated silica. , Silicic anhydride, carbon black, calcium carbonate, clay,
Talc, titanium oxide, magnesium carbonate, quartz, aluminum fine powder, flint powder, zinc dust, polyethylene,
Polypropylene, high styrene resin, cyclized rubber, cumarone-indene resin, phenol-formaldehyde resin, modified melamine resin, petroleum resin, styrene copolymer,
Lignin and the like. Among these fillers, precipitated silica, fumed silica, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable. These fillers may be used alone or in combination of two or more.

Examples of the flexibility control agent include polybutene, polybutadiene, and non-reactive polyisobutylene.

The antioxidants include phenolic antioxidants, aromatic amine antioxidants, sulfur hydroperoxide decomposers, phosphorus hydroperoxide decomposers,
Examples include benzotriazole-based UV absorbers, salicylate-based UV absorbers, benzophenone-based UV absorbers, hindered amine-based light stabilizers, and nickel-based light stabilizers.

Specific examples of the phenolic antioxidants include 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, and 2,6-di-t-butyl-4.
-Methylphenol, 2,5-di-t-butylhydroquinone, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate],
2,2′-methylenebis (4-methyl-6-t-butylphenol), 4,4′-butylidenebis (3-methyl-6-t-butylphenol), 4,4′-thiobis (3-methyl-6-t -Butylphenol) and the like.

Specific examples of the aromatic amine antioxidant include N, N'-diphenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-
Examples thereof include dihydroquinoline.

Specific examples of the sulfur-based hydroperoxide decomposer include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate. Pionate and the like can be exemplified.

Specific examples of the phosphorus hydroperoxide decomposer include diphenylisooctyl phosphite,
Examples include triphenyl phosphite.

Specific examples of the benzotriazole-based ultraviolet absorber include 2- (3,5-di-tert-butyl-2-).
(Hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2-
(3,5-di-t-butyl-2-hydroxyphenyl)
Benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole and the like can be exemplified.

Specific examples of the salicylate-based ultraviolet absorber include 4-t-butylphenyl salicylate,
Examples thereof include 4-di-t-butylphenyl-3,5′-di-t-butyl-4′-hydroxybenzoate.

Specific examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone,
-Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, and the like.

Specific examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4
-Piperidyl) sebacate, bis (1,2,2,6,
6, -pentamethyl-4-piperidyl) sebacate, 1
-{2- [3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl} -4-
[3- (3,5-Di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,
6,6, -tetramethylpiperidine and the like can be exemplified.

Specific examples of the nickel light stabilizer include nickel dibutyldithiocarbamate, [2,2
'-Thiobis (4-t-octylphenolate)]-2
-Ethylhexylamine nickel (II), [2.2
'-Thiobis (4-t-octylphenolate)]-n
-Butylamine nickel (II) and the like.

These antioxidants may be used alone or in combination of two or more. It may work more effectively when used in combination than when used alone.

Specific examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- ( 2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2
-Aminoethyl) aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-
Benzyl-γ-aminopropyltrimethoxysilane, N
Amino-containing silanes such as -vinylbenzyl-γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane Mercapto group-containing silanes such as silane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Epoxy group-containing silanes such as trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2
Carboxysilanes such as -methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ Silanes containing a vinyl-type unsaturated group such as acroyloxypropylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; -Containing isocyanate groups such as isocyanate propyl trimethoxy silane, γ-isocyanate propyl triethoxy silane, γ-isocyanate propyl methyl diethoxy silane, and γ-isocyanate propyl methyl dimethoxy silane. Silanes and the like. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated amino silane complexes, blocked isocyanate silanes, phenylamino long-chain alkyl silanes, amino silylated silicones, silylated polyesters, and the like, which are modified derivatives thereof, are also used as silane coupling agents. Can be used.

The silane coupling agent may be used alone or in combination of two or more.

In the hot melt composition of the present invention, an adhesion-imparting agent other than the silane coupling agent can be used.

The hot-melt composition of the present invention can be used in various applications as a hot-melt composition which has little property deterioration at high temperatures and is easy to produce, as an alternative to conventional hot-melt products, It is molded into a body, an adhesive, or a foam, and can be used for, for example, an adhesive material, a gasket material, a sealing material, a base material for an adhesive, a molding material, a rubber material, and the like. More specifically, there are exemplified sealing materials for construction, vehicles, rubber-like spacers for double glazing, waterproof seals for automobiles, waterproofing tapes for construction, electrical insulating tapes, various packings, and the like.

When the hot melt composition of the present invention is used as a rubber-like spacer for double glazing, a desiccant-containing spacer is added to the hot melt composition comprising the components (A) and (B) of the present invention. Examples include a method of using a hot melt composition containing a desiccant component as a component (C) in addition to the component (A) and the component (B) of the present invention. Tokiko Sho 63
-50508, Japanese Patent Application Laid-Open No. 9-295838, etc., in which a solid spacer is used in combination to maintain the glass interval. As a part of the component (B), the elastic modulus at room temperature such as polyethylene is used. In order to contain a high component, a method of maintaining a glass interval without a solid spacer is effective, and in any method, by using the hot melt composition of the present invention, a decrease in characteristics at high temperatures is small. In addition, it is possible to produce a double glazing which is easy to produce.

[0081]

Embodiments of the present invention will be described below. Example 1 As the component (a), a reactive silicon group-containing polyisobutylene (Epion EP303S manufactured by Kaneguchi Chemical Co., Ltd.) 2
0 parts is butyl rubber (Exxon butyl 065 manufactured by Exxon Chemical) which is a hot melt resin of the component (B).
Part, 40 parts of paraffin-based process oil (PS-32, manufactured by Idemitsu Kosan Co., Ltd.) as a plasticizer of component (B), and 60 parts of tackifier (Escolets # 1304, manufactured by Exxon Chemical) as an additional additive, antioxidant ( 1 part of Adeka Argus mark AO-50) 1 part, 150 parts of calcium carbonate filler (white stone SB red made of Shiroishi calcium)
As a component for reacting a reactive silicon group, water 2 parts
After kneading at 120 ° C. in a kneader-type kneader, 0.6 part of a silanol curing catalyst (Nitto Kasei U-220) is added, and then kneading is further continued to reduce at least the substantial crosslinking point. An organic polymer cured product (A) partially having a siloxane bond was obtained. By dissolving the composition in toluene and generating a gel, it was confirmed that the component (A) could be synthesized by curing the component (a).

Next, the holding force was measured according to JIS Z0237. The hot melt composition is heated at 100 ° C.
Thickness obtained by compression molding on a polyester sheet with
The adhesive sample of 00 μm was adhered to the chromium-treated aluminum so as to have an adhesive area of 25 × 25 mm, and the holding force at 80 ° C. under a static load of 200 g was measured. As a result, it was 100 minutes or more. Example 2 The component (a) of Example 1 contained 40 parts, water 4 parts,
An adhesive sample prepared under the same conditions as in Example 1 except that the amount of the silanol curing catalyst was 1.2 parts was measured for a holding force at 80 ° C., and as a result, it was 100 minutes or more. Comparative Example 1 A pressure-sensitive adhesive sample prepared under the same conditions as in Example 1 except that the component (a) of Example 1, water and a silanol curing catalyst were added, was measured for holding power at 80 ° C. Fell in minutes. Example 3 As a component (a), 100 parts of a reactive silicon group-containing polyisobutylene having a molecular weight of about 16,000,
(B) 30 parts of process oil (PS-32 manufactured by Idemitsu Kosan) as a plasticizer as a component, and calcium carbonate filler (whiten SB made of Shiroishi calcium) as another additive
Red) 40 parts, silane coupling material (A-1122 manufactured by Nippon Unicar) 3 parts, water 4 parts as a component for reacting a reactive silicon group, silanol curing catalyst (Nitto Kasei)
U-220) 3 parts were mixed and allowed to stand at 23 ° C. for 1 day and at 50 ° C. for 3 days, whereby an organic polymer cured product (A) component in which at least a part of substantial crosslinking points was a siloxane bond Was synthesized. From the initial liquid state of the composition,
It was confirmed that the component (A) could be synthesized by curing the component (a) by becoming a rubber-like cured product. 13.9 parts of the cured product and butyl rubber (Exxon butyl 065 manufactured by Exxon Chemical) as a hot melt resin of the component (B)
31.1 parts were kneaded in a kneader-type kneader at 160 ° C., and then the thermoplastic resin (B), polyethylene (Novalac HD-HJ490, manufactured by Nippon Polychem) 9.7.
Part, zeolite 4A 1 which is a desiccant substance of component (C)
8.4 parts, as other additives, 18.4 parts of talc (LMR manufactured by Tsuchiya Kaolin), 7.9 parts of tackifier (ESCORETS # 1304 manufactured by Exxon Chemical), antioxidant (Mark AO-50 manufactured by Adeka Argus) 0 By adding 0.5 part and kneading, a hot melt composition was obtained. As a result of press-molding the hot melt composition at 180 ° C., good moldability was exhibited. As a result of performing a strength comparison at 23 ° C./80° C. using this molded body, the retention was about 80%. Example 4 In Example 3, the synthesized cured product was 7.3.
Parts, butyl rubber: 37.0 parts, polyethylene: 10.3
A hot melt composition was prepared under the same conditions as in Example 3 except that the composition was a part, and press-molding at 180 ° C. showed good moldability. 23 ° C./8 using this molded body
As a result of carrying out a strength comparison at 0 ° C., the retention was about 70%. Comparative Example 2 In Example 3, instead of adding the cured product containing the component (A) of the present invention, butyl rubber was added to 55.0.
The hot melt composition was prepared under the same conditions as in Example 3 and Example 3, and a strength comparison at 23 ° C./80° C. was performed using a press-formed product at 180 ° C.
The retention was about 50%.

[0083]

According to the present invention, it is possible to obtain a hot-melt composition which is less likely to deteriorate at high temperatures and can be easily manufactured. As an alternative to the conventional hot-melt products, a pressure-sensitive adhesive material, a gasket material It can be used for sealing materials, base materials for adhesives, molding materials, rubber materials, etc., especially as a rubber-like spacer for multilayer glass, making it possible to produce multilayer glass with improved long-term reliability. it can.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 91/00 C08L 91/00 C09J 5/06 C09J 5/06 201/10 201/10 201/10 F term (reference) 4J002 AC11W AE043 AE053 BB00X BB033 BB10W BB133 BB18X BB183 BB20W BB22X BC02X BD03X BD12X BE03X BG02X BL013 BP01X CD163 CP17W DE147 DG057 DJ007 DJ017 EA016 EA026 EH046 EH096 EH126 EH146 EH156 EW046 FD023 FD026 GJ01 GJ02 4J040 CA171 CA172 DA001 DA002 DB001 DB002 DC091 DC092 DD001 DD002 DE001 DE002 DF001 DF002 ED001 ED002 EF001 EF002 EG001 EG002 GA31 HA136 HA256 HA306 HB01 HB02 HB03 HB04 HB32 HB34 HB44 HD24 JA06 JB01 KA31 KA43 LA08 MA05 MB04 MB09 NA12

Claims (13)

[Claims] 1. A hot melt composition containing an organic polymer cured product (A) in which at least a part of substantial crosslinking points is a siloxane bond. 2. The hot melt composition according to claim 1, wherein the component (B) contains one or more components selected from a hot melt resin, a thermoplastic resin and a plasticizer. Item 7. The hot melt composition according to Item 1. 3. The hot melt composition according to claim 1, further comprising a desiccant substance or a hygroscopic substance as the component (C). object. 4. The cured organic polymer as the component (A) has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and has at least one silicon-containing group which can be crosslinked by forming a siloxane bond. The hot melt composition according to any one of claims 1 to 7, wherein the composition is obtained by curing the organic polymer (a). 5. The hot melt composition according to claim 1, wherein the organic polymer as the component (a) is a saturated hydrocarbon polymer. 6. The hot melt resin as the component (B) is a hot melt resin selected from butyl rubber, polyisobutylene, styrene block polymer, EVA, olefin, polyester, and polyamide.
The hot melt composition according to the above. 7. The hot melt composition according to claim 1, wherein the thermoplastic resin (B) is a thermoplastic resin selected from a polyolefin resin, a polystyrene resin, a vinyl chloride resin, an acrylic resin, and a fluororesin. 8. The hot melt resin according to claim 1, wherein the plasticizer (B) is a plasticizer selected from polybutene, process oil and ester plasticizer. 9. The hot melt composition according to claim 1, which is obtained by mixing a composition containing the component (A) and a composition containing the component (B). A method for producing a hot melt composition. 10. The hot melt composition according to claim 1, wherein the organic polymer as the component (a) is cured in a composition containing the component (B), and the organic polymer as the component (A) is cured. A method for producing a hot melt composition, which is obtained by synthesizing a united cured product. 11. An adhesive material containing the hot melt composition according to claim 1. 12. A rubber spacer for a double glazing obtained by molding the hot melt composition according to claim 1. 13. A double glazing, wherein the outer peripheral end of the rubber spacer according to claim 12 is disposed flush with the outer peripheral end of the glass plate.