WO2006088112A1

WO2006088112A1 - Reactive resin composition

Info

Publication number: WO2006088112A1
Application number: PCT/JP2006/302777
Authority: WO
Inventors: Hiroshi Ito
Original assignee: Kaneka Corporation
Priority date: 2005-02-21
Filing date: 2006-02-16
Publication date: 2006-08-24
Also published as: JPWO2006088112A1

Abstract

Disclosed is an adhesion composition for a hardly adhesive substrate, which has a sufficient adherability on a hardly adhesive substrate. A reactive resin composition comprising (A) an organic polymer having a reactive silicon group at a ratio of 0.8 group or more in average per molecule, (B) a crosslink-controlling agent, (C) a catalyst, and (D) a filler. The crosslink-controlling agent includes: (B-i) a silicone compound having one Si atom in the molecule and also having a hydroxyl group or groups and a hydrolysable group or groups attached to the Si atom, provided that the total number of the hydroxyl group(s) and the hydrolysable group(s) is 1 or 2; (B-ii) a silicone compound having 2 to 20 Si atoms in the molecule and also having a hydroxyl group or groups and a hydrolysable group or groups attached to any of the Si atoms, provided that the total number of the hydroxyl group(S) and the hydrolysable group(S) attached to all of the Si atoms in the molecule is 2 or 5 and the total number of the hydroxyl group and the hydrolysable group attached to each Si atom is 0 or 1; and (B-iii) a silicone compound represented by the general formula (1). R4-NH-R1-Si(R2)z(R3)3-z (1)

Description

Specification

Reactive resin composition

Technical field

[0001] The present invention relates to a reactive silicon group-containing organic compound having an average of 0.8 or more of a key group-containing functional group (hereinafter also referred to as "reactive key group") that forms a siloxane bond. The present invention relates to a reactive resin composition containing a polymer, a bridge adjusting agent, a catalyst and a filler. The present invention also relates to an adhesive particularly suitable for a conventionally difficult-to-bond substrate such as a polyolefin substrate.

Background art

[0002] It is known that an organic polymer having a reactive cage group in a molecule exhibits reactivity when the reactive cage group is hydrolyzed by moisture to form a siloxane bond. .

[0003] Among these polymers having a reactive cage group, a polymer whose main chain is polyoxyalkylene and a polymer whose main chain is polyisobutylene have already been industrially produced and are sealing materials. Widely used in applications such as adhesives, injection materials, putty materials and paints.

[0004] In these applications, adhesion to various materials is required. For adhesion, for example, adhesion such as silane coupling agent (Patent Document 1) and titanium coupling agent (Patent Document 2) is applied. Additives have been added to improve adhesion. In addition, an epoxy resin (Patent Document 3) and an acrylic resin (Patent Document 4) compatible with an organic polymer having a reactive silicon group have been added to improve adhesion.

[0005] Polyolefin materials that are stronger and more recyclable and safer materials, such as polyethylene, polypropylene, ethylene propylene terpolymer (EPDM), etc., or mixed molded articles containing any of these polyolefin materials In the case of using an adherend as a material such as this, it is difficult to bond, and it has been difficult to satisfy the required characteristics of adhesiveness with conventional techniques.

Patent Document 1: JP-A 57-182350

Patent Document 2: JP 59-24771

Patent Document 3: Japanese Patent Laid-Open No. 61-268720 Patent Document 4: JP-A 63-112642

Disclosure of the invention

Problems to be solved by the invention

[0006] The main object of the present invention is to provide an adhesive composition for difficult-to-adhere substrates that can provide sufficient adhesive strength to difficult-to-adhere substrates that are difficult to adhere by conventional adhesion techniques.

Means for solving the problem

[0007] As a result of intensive investigations in view of the above circumstances, the present inventors have used a composition that can reduce the gel fraction of the resin component containing an organic polymer having a reactive key group. The present inventors have found that it is possible to ensure adhesion performance to a difficult-to-adhere substrate and have reached the present invention.

That is, the present invention provides:

(1) Contains an organic polymer (A) having an average of 0.8 or more reactive key groups per molecule (A), bridge modifier (B), catalyst (C) and filler (D) A reactive resin composition, and an adhesive using the same.

(2) Preferably, the reactive resin composition having an average of 0.8 to 1.4 reactive key groups in the component (A), and an adhesive using the same.

(3) Preferable as a crosslinking regulator (B)

(B—i) A silicon compound in which the number of silicon atoms in the molecule is one and the total number of hydroxyl groups and hydrolyzable groups bonded to the silicon atom is one or two (where hydrolysis The functional group is a group that can react with moisture to form a silanol group together with a silane atom)

(B-ii) The number of silicon atoms in the molecule is 2 to 20, the total number of hydroxyl groups and hydrolyzable groups bonded to any silicon atom in the molecule is 2 to 5, and each silicon A silicon compound in which the total number of hydroxyl groups and hydrolyzable groups bonded to the same silicon atom is 0 or 1, and

(B-iii) Silicone compound of the following formula (1)

R ⁴ — NH— R ¹ — Si (R ² ) (R ³ ) (1)

z 3-z

(Where R ¹ is a branched or cyclic alkylene group, an arylene group, an alkali monolene group or an alcoholylalkylene group, and when R ¹ has 4 or more carbon atoms, these groups are! Also, the deviation may contain one or more oxygen atoms or (poly) sulfide bonds. . R ² is an alkyl group having 1 to 6 carbon atoms, an aryl or alkaryl group having 5 to 20 carbon atoms. R ³ is a C1 to C6 alkoxy group or a C3 to C5 ketoximate group. R ⁴ is a hydrogen or hydrocarbon group, or a group that thermally desorbs to form an amine group containing a nitrogen atom to which it is bonded, and z is 0 or 1.) .

(Alkali monoene group refers to a divalent hydrocarbon group in which one of the bonds is on the aryl group and the other is on the alkyl group. The alkaryl group is a bond on the aryl group. An aryl group having an alkyl group present.)

(4) The preferred amount of filler (D) is 10 to 300 parts by weight with respect to 100 parts by weight of the organic polymer (A).

(5) Organic polymer The main chain skeleton of (A) is preferably an alkylene oxide polymer.

(6) The number average molecular weight of the organic polymer (A) is from 10,000 to 10,000.

[0009] The composition of the present invention is based on the total amount of (A) component, (B) component and (C) component of a cured product obtained by curing for 8 days at room temperature and normal humidity. It is preferable that the gel fraction is adjusted to be less than 20% by weight.

The invention's effect

[0010] An adhesive comprising the composition of the present invention has a sufficient adhesive strength to a polyolefin base material, which is conventionally known as a difficult adhesion base material due to its strength, and is difficult to adhere. It is particularly useful as a substrate attachment composition.

BEST MODE FOR CARRYING OUT THE INVENTION

[0011] The main chain skeleton of the organic polymer (A) having 0.8 or more reactive cage groups in one molecule used in the present invention has various main chain skeletons that are not particularly limited. be able to.

[0012] Specific examples of the main chain skeleton include polyoxyalkylene polymers, hydrocarbon polymers, polyester polymers, (meth) acrylate (co) polymers, vinyl polymers, graft weights Examples thereof include a polymer, a polysulfide polymer, a polyamide polymer, and a polycarbonate polymer.

[0013] Examples of the polyoxyalkylene polymer include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene polyoxypro Examples include pyrene copolymers and polyoxypropylene polyoxybutylene copolymers.

[0014] Hydrocarbon polymers include ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene, butadiene and acrylonitrile, and Z or styrene. Copolymers of polybutadiene, isoprene or butadiene with acrylonitrile, styrene, etc.

Examples thereof include hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers.

[0015] Examples of the polyester-based polymer include a condensation polymer of dibasic acid such as adipic acid and Daricol, or a ring-opening polymer of ratatones, and examples thereof include terephthalic acid, isophthalic acid and bisphenol. Examples thereof include a diallyl phthalate polymer obtained by condensation polymerization with A.

[0016] (Meth) acrylic acid ester-based (co) polymers include ethyl (meth) acrylate, butyl

Examples thereof include polymers obtained by radical polymerization of monomers such as (meth) acrylate.

[0017] Examples of other bulle polymers include polymers obtained by radical polymerization of monomers such as butyl acetate, acrylonitrile, and styrene.

[0018] Examples of the graft polymer include polymers obtained by reacting an organic polymer with a vinyl monomer.

[0019] The polyamide polymer includes nylon 6 obtained by ring-opening polymerization of ε-strength prolatatam, nylon 6 · 6 obtained by condensation polymerization of hexamethylenediamine and adipic acid, and hexamethylenediamine. Nylon 6 · 10 obtained by polycondensation of sebacic acid, Nylon 11 obtained by polycondensation of ε-aminoundecanoic acid, Nylon 12 obtained by ring-opening polymerization of ε-aminolaurac ratatatam, and 2 of the above nylons Copolymer nylon etc. which have a component more than a component are mentioned.

[0020] Examples of the polycarbonate-based polymer include a polymer obtained by condensation polymerization of bisphenol and chlorochloride.

[0021] Among the polymers having the main chain skeleton, a polyoxyalkylene polymer, a hydrocarbon polymer, a polyester polymer, a (meth) acrylic ester (co) polymer, a polycarbonate Nate polymers are preferred because they are readily available and manufactured.

[0022] Further, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester copolymers have relatively high glass transition temperatures. Is particularly preferred because it is excellent in cold resistance.

[0023] Furthermore, the polyoxyalkylene polymer is most preferable from the viewpoint of good workability and a high degree of freedom in the compounding system.

[0024] The main chain skeleton of the organic polymer (A) may contain other components such as a urethane bond component as long as the effects of the present invention are not significantly impaired.

[0025] The urethane-binding component is not particularly limited, and examples thereof include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; Reacting power of polyisocyanate compounds such as aliphatic polyisocyanates such as isocyanates and hexamethylene diisocyanates and polyols having various main chain skeletons, etc. Can be mentioned.

[0026] The reactive group contained in component (A) has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and is a group capable of forming a siloxane bond by a reaction accelerated by a silanol condensation catalyst. It is. Reactive key groups include general formula (2):

One (SiR ⁵ XO) -SiR ⁶ X (2)

2— b b m 3— a a

(Wherein R ⁵ and R ⁶ are the same or different alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) SiO—. bird

Three

When an organosiloxy group is present and two or more R ⁵ or R ⁶ are present, they may be the same or different. Here, R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, they may be the same or different. a represents 0, 1, 2 or 3, and b represents 0, 1, or 2. M (SiR ⁵

2-

For b in the X O) group, they may be the same or different. m b b

Indicates an integer from 0 to 19. Provided that a + ∑b≥l is satisfied). [0027] The hydrolyzable group is not particularly limited and may be any conventionally known hydrolyzable group! Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkalkoxy group. Among these, hydrogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, aminooxy groups, mercapto groups and alkenyloxy groups are preferred because of their mild hydrolyzability and handling! Viewpoint power An alkoxy group is particularly preferred.

[0028] The hydrolyzable group or the hydroxyl group can be bonded to one key atom in the range of 1 to 3, and (a + ∑b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded in the reactive cage group, they may be the same or different.

[0029] In particular, the general formula (3):

-SiR ⁶ X (3)

3-a a

(Wherein R ⁶ and X are the same as described above, and a is an integer of 1 to 3).

[0030] Specific examples of R ⁵ and R ⁶ in the above general formulas (2) and (3) include alkyl groups such as a methyl group and an ethyl group, cycloalkyl groups such as a cyclohexyl group, and phenols. An aryl group such as a group, an aralkyl group such as a benzyl group,

R 'is a methyl group, a phenyl group, or the like (R') Triorganosiloxy group represented by SiO-

Three

Can be given. Of these, the methyl group is particularly preferred!

[0031] More specific examples of reactive silicon groups include trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, methyldimethoxysilyl, methyljetoxysilyl, methyldiisopropo A xylyl group may be mentioned.

[0032] The introduction of the reactive cage group to the component (A) may be performed by a known method. For example, the following methods can be mentioned.

[0033] (ii) An organic polymer having a functional group such as a hydroxyl group in the molecule is reacted with an organic compound having an active group and an unsaturated group that are reactive to the functional group, and contains an unsaturated group. To obtain an organic polymer. Alternatively, for example, when an epoxide is ring-opening polymerized to obtain an organic polymer, the unsaturated group-containing epoxide is subjected to ring-opening copolymerization to produce an unsaturated group-containing organic polymer. An unsaturated group-containing organic polymer is obtained by copolymerizing a monomer having an unsaturated group that does not participate in the polymerization reaction. Next, the resulting reaction product is hydrosilylated by allowing hydrosilane having a reactive silicon group to act.

[0034] (Mouth) An organic polymer containing an unsaturated group obtained in the same manner as in the method (i) is reacted with a compound having a mercapto group and a reactive key group.

(C) A compound having a functional group reactive to this functional group and an organic group having a reactive group in an organic polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in the molecule. React.

[0036] Among the above methods, the method (i) or the method (c) in which a polymer having a hydroxyl group at the terminal is reacted with a compound having an isocyanate group and a reactive group is comparative. It is preferable because a high conversion rate can be obtained in a short reaction time. Furthermore, the organic polymer having a reactive group obtained by the method (i) has a lower viscosity and a better workability than the polymer obtained by the method (c). The polymer obtained by the (mouth) method has a strong odor based on mercaptosilane, and therefore the method (i) is particularly preferred.

[0037] Specific examples of the hydrosilane compound used in the method (i) include, for example, halogenosilanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; Alkoxy silanes such as ethoxysilane, methyl jetoxy silane, methyl dimethoxy silane, and phenyl dimethoxy silane; (Cyclohexyl ketoximate) Forces including ketoximate silanes such as methyl silane are not limited to these. Of these, halogenated silanes and alkoxysilanes are particularly preferred. In particular, alkoxysilanes are most preferred because of the mild hydrolyzability of the resulting composition!

[0038] (Mouth) can be synthesized, for example, by an organic polymer unsaturated bond by radical addition reaction of a compound having a mercapto group and a reactive cage group in the presence of a radical initiator and Z or a radical source. The method of introduction into the site can be mentioned, but it is not particularly limited. A compound having a mercapto group and a reactive cage group Examples of power include, for example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylpyrumethyldimethoxysilane, γmercaptopropyltriethoxysilane, γmercaptopropylmethyljetoxysilane, and the like. Absent.

[0039] In the synthesis method (c), as a method of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive group, for example, a method disclosed in JP-A-3-47825 is disclosed. There is no particular limitation. Specific examples of the compound having an isocyanate group and a reactive silicon group include, for example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, γisocyanatepropyltriethoxysilane, γ-Isocyanate propinolemethylethyloxysilane and the like are not limited thereto.

[0040] Component (Α) may be linear or branched, and its number average molecular weight is preferably about 10,000 to 100,000 in terms of polystyrene in GPC, more preferably 15,000- 50,000. If the number average molecular weight is less than 10,000, the composition has a high hardness, which is inconvenient. If the number average molecular weight exceeds 100,000, the viscosity tends to be high, which tends to be inconvenient.

[0041] The reactive cage group may be at the end or inside of the organic polymer molecular chain,

May be both terminal and internal. In particular, when a reactive cation group is present only at the molecular end, a network of polymer components contained in the composition is efficiently constructed, so that an effective amount of network can be achieved with a small amount of reactive cation group. It is preferable because it can be obtained.

[0042] There are various methods for measuring the introduction rate of reactive cage groups, but at present, the integral value of the terminal at which the reactive cage group was introduced by the ¹ Η-NMR ^ vector. Force can be calculated.

[0043] There is a method of measuring the gel fraction in order to measure the amount of network formation. As a method for measuring the gel fraction, a method is generally used in which a cured product wrapped with a wire mesh or the like is placed in a solvent in which a polymer dissolves, and the amount of gel remaining without extraction is measured.

[0044] The polyoxyalkylene polymer essentially has the general formula (4):

R ⁷ — Ο— (4) (Wherein R ⁷ is a linear or branched alkylene group having 1 to 14 carbon atoms), and R ⁷ in the general formula (4) is branched. The number of carbon atoms preferred by the alkylene group is more preferably 2-4. Specific examples of the repeating unit represented by the general formula (4) are as follows:

-CH O-, -CH CH O-, -CH CH (CH) θ-

2 2 2 2 3

-CH CH (C H) 0—, — CH C (CH) —O-

2 2 5 2 3 2

CH CH CH CH O—

2 2 2 2

Etc.

[0045] The main chain skeleton of the polyoxyalkylene polymer may have only one type of repeating unit force, or may have two or more types of repeating unit forces. In particular, the polymer having a propylene oxide polymer as a main component is preferable because it is amorphous and has a relatively low viscosity.

[0046] As a method for synthesizing a polyoxyalkylene polymer, for example, a polymerization method using an alkali catalyst such as KOH, obtained by reacting an organoaluminum compound and porphyrin disclosed in JP-A-61-215623 can be obtained. Transition metal compounds such as complex-polymerization method using Borhuylin complex catalyst, JP 46-27250, JP 59-15336, US Patent 327845 7, US Patent 3278458, US Patent 3278459, US Patent 3427256 A polymerization method using a composite metal cyanide complex catalyst as shown in US Pat. No. 3,427334, US Pat. No. 3,427335, etc., a polymerization method using a catalyst which is also a polyphosphazene salt exemplified in JP-A-10-273512, Examples thereof include, but are not limited to, a polymerization method using a catalyst having a phosphazene compound power exemplified in Kaihei 11-060722.

[0047] A method for producing a polyoxyalkylene polymer having a reactive key group is disclosed in JP-B-45.

-36319, 46-12154, JP-A-50-156599, 54-6096, 55

— 13767, 55—13468, 57—164123, JP 3-2450, US Patent 3632557, US Patent 4345053, US Patent 4366307, US Patent 4960844, etc. JP-A-61-197631, 61-215622, 61-215623, 61-218632, JP-A-3-72527, JP-A-3-47825

The number average molecular weight proposed in JP-A-8-231707 is 6,000 or more, Mw ZMn has a high molecular weight of 1.6 or less, a narrow molecular weight distribution, and a power that can be exemplified by a polyoxyalkylene polymer.

[0048] The above-mentioned polyoxyalkylene polymer having a reactive silicon group may be used alone or in combination of two or more.

[0049] The saturated hydrocarbon polymer is a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and the polymer constituting the skeleton thereof is (1) ethylene, propylene, 1-butene, The ability to polymerize olefin-based compounds having 1 to 6 carbon atoms such as isobutylene as the main monomer, (2) homopolymerization of gen-based compounds such as butadiene and isoprene, or the above-mentioned olefin-based compounds Force that can be obtained by methods such as hydrogenation after polymerization Isobutylene-based polymers and hydrogenated polybutadiene-based polymers immediately introduce functional groups at the ends and immediately control the molecular weight. From the viewpoint of ease of synthesis, which is preferable, an isobutylene polymer is particularly preferable.

[0050] Those whose main chain skeleton is a saturated hydrocarbon polymer have characteristics of excellent heat resistance, weather resistance, durability, and moisture barrier properties.

[0051] In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units or may be a copolymer with other monomers, but the surface property of rubber characteristics is derived from isobutylene. Those containing 50% by weight or more of repeating units are preferred. Those containing 80% by weight or more are more preferred. Those containing 90 to 99% by weight are particularly preferred.

[0052] As a method for synthesizing a saturated hydrocarbon polymer, various polymerization methods have been reported.

1S Many so-called living polymerizations have been developed especially in recent years. In the case of saturated hydrocarbon polymers, especially isobutylene polymers, Y-Fer polymerization found by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, 15 、, 2843) can be easily produced, and it is known that a molecular weight of about 500 to 100,000 can be polymerized with a molecular weight distribution of 1.5 or less, and various functional groups can be introduced at the molecular ends. It has been.

[0053] Examples of the method for producing a saturated hydrocarbon polymer having a reactive silicon group include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, and JP-A-64. - twenty two The forces described in JP-A No. 904, JP-A-1-197509, JP-A-2539445, JP-A-2873395, JP-A-7-53882 are not particularly limited to these.

[0054] The saturated hydrocarbon-based polymer having a reactive cage group may be used alone or in combination of two or more.

[0055] In the present invention, as the organic polymer of component (A), one having a molecular chain of a (meth) acrylic acid ester copolymer can be used.

[0056] The (meth) acrylic acid ester monomer constituting the main chain of the (meth) acrylic acid ester polymer is not particularly limited, and various types can be used. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylic acid isobutyl, (meth) acrylic acid tert-butyl, (meth) acrylic acid n-pentyl, (meth) acrylic acid n xylyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid n- Heptyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Noel (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylate -Ru, (meth) acrylic acid toluyl, (meth) acrylic acid benzyl, (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 3-methoxybutyl Cyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, _Ύ — (methacryloyl Oxypropyl) trimethoxysilane, (meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethylmethyl, (meth) acrylic acid 2-trifluoromethylethyl, (meth) acrylic Acid 2-perfluoroethyl, (meth) acrylic acid 2-Perfluoroethyl 2-perfluorobutylethyl, (meth) acrylic 2-perfluoroethyl, (meth) a Perfluoromethyl crylate, diperfluoromethyl methyl (meth) acrylate, (meth) acrylic acid 2-perfluoromethyl 2- -(Meth) acrylic such as fluorethylmethyl, (meth) acrylic acid 2 perfluro-hexylethyl, (meth) acrylic acid 2-perfluorodecylethyl, (meth) acrylic acid 2-perfluoro-hexadecylethyl Examples include acid monomers. In the (meth) acrylic acid ester copolymer, (meth) acrylic acid The following bull monomers can be copolymerized with the ester monomers. Examples of the butyl monomers include styrene monomers such as styrene, butyltoluene, monomethylstyrene, chlorostyrene, styrene sulfonic acid and salts thereof; fluorine such as perfluoroethylene, perfluoropropylene and vinylidene fluoride. Containing butyl monomers; butyl-containing butyl monomers such as butyltrimethoxysilane and butyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid and Dialkyl ester; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cycl Maleimide monomers such as hexylmaleimide; -Tolyl group-containing butyl monomers such as acrylonitrile and methacrylonitrile; Amide group-containing butyl monomers such as acrylamide and methacrylamide; Acetyl butyl, propionate, pivalate, Bull esters such as benzoic acid bull and cinnamic acid bull; Alkenes such as ethylene and propylene; Conjugates such as butadiene and isoprene; Bulle chloride, vinylidene chloride, allyl chloride, aryl alcohol, etc. It is done. These may be used alone or a plurality of these may be copolymerized. Of these, a polymer composed of a styrene monomer and a (meth) acrylic acid monomer is preferable in view of the physical properties of the product. More preferably, it is a (meth) acrylic polymer composed of an acrylic ester monomer and a methacrylic ester monomer, particularly preferably an acrylic polymer that also has an acrylic ester monomer power, and even more preferably a ptylca acrylate. It is a polymer. In the present invention, these monomers are preferably copolymerized with other monomers, and further block copolymerized, and in this case, these preferable monomers may be contained in a weight ratio of 40%. preferable. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and Z or methacrylic acid.

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

[0058] Among the living radical polymerization methods, an atom transfer radical polymerization method is preferred in which a (meth) acrylate-based monomer is polymerized using an organic halide or a halogenated sulfol compound as an initiator and a transition metal complex as a catalyst. . In addition to the characteristics of the above-described living radical polymerization method, this method is a method for obtaining a polymer having a halogen or the like that is relatively advantageous for functional group conversion reaction at the terminal, and designing the initiator and catalyst. Since the degree of freedom is large, it is suitable as a method for producing a (meth) acrylic acid ester-based copolymer having a reactive cage group. Examples of this atom transfer radical polymerization method include the method shown in Matyjaszewski et al., Journal 'Ob' American 'Chemical Society (J. Am. Chem. Soc.) 1995, 117 卷, page 5614. .

[0059] For example, Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, and Japanese Patent Application Laid-Open No. Hei 6-211922 are methods for producing a (meth) acrylic acid ester-based copolymer having a reactive cage group. A gazette discloses a production method using a free radical polymerization method using a chain transfer agent. Further, the power disclosed in JP-A-9-272714 and the like using a method using an atom transfer radical polymerization method is not particularly limited thereto.

[0060] The reactive cage group of component (A) may be at the end or inside of the organic polymer molecular chain, or may be at both the end and inside. In particular, when the reactive chain group is only at the end of the polymer main chain, the amount of effective network chain of the polymer component finally formed in the composition increases, so that a small amount of reactive chain is present. I also like the point power that makes it easy to obtain an effective amount of mesh with the base amount.

[0061] As a polymerization method of the component (A), when a living radical polymerization method is used, the molecular weight distribution is narrow and the viscosity is low, and a crosslinkable functional group can be introduced into the molecular chain terminal at a high rate. Among them, the atom transfer radical polymerization method is particularly preferable among these.

[0062] The (meth) acrylic acid ester-based copolymer having a reactive cage group may be used alone or in combination of two or more.

[0063] A polyoxyalkylene polymer having a reactive key group and a reactive key group A method for producing an organic polymer obtained by blending a (meth) acrylic acid ester copolymer is described in JP-A-59-122541, JP-A-63-112642, JP-A-6-172631, and JP-A-11-11. — The power proposed in the 116763 gazette etc. It is not limited to these.

[0064] Preferred examples of the (meth) acrylic acid ester copolymer of component (A) are specific examples of U ヽ, having a reactive cage group and a molecular chain substantially having the following general formula (5):

-CH -C (R ⁸ ) (COOR ⁹ ) (5)

2

(Wherein R ⁸ represents a hydrogen atom or a methyl group, R ⁹ represents an alkyl group having 1 to 9 carbon atoms) (meth) acrylate monomer having an alkyl group having 1 to 9 carbon atoms Unit and general formula (6) below:

-CH -C (R ⁸ ) (COOR ¹⁰ ) (6)

2

(Wherein R ⁸ is the same as described above, R ^1C> represents an alkyl group having 10 or more carbon atoms) and has a (meth) acrylate monomer unit strength having an alkyl group having 10 or more carbon atoms In this method, the copolymer is blended with a polyoxyalkylene polymer having a reactive silicon group.

[0065] R ^{9 in the} general formula (5) is, for example, 1-9 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a 2-ethylhexyl group, preferably Examples of the alkyl group include 1 to 4, and more preferably 1 to 2. The alkyl group for R ⁹ may be used alone or in combination of two or more.

[0066] R ^1G of the general formula (6) is, for example, 10 or more carbon atoms such as lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group, etc., usually 10 to 30, preferably 10 -20 long chain alkyl groups. The alkyl group for R ^1G may be used alone or in a mixture of two or more as in the case of R ⁹ .

[0067] The molecular chain of the (meth) acrylic acid ester-based copolymer substantially has a monomer unit force of the formula (5) and the formula (6). This means that the sum of the monomer units of formula (5) and formula (6) present in the copolymer exceeds 50% by weight. The total of the monomer units of the formula (5) and the formula (6) is preferably 70% by weight or more.

[0068] The ratio of the monomer unit of the formula (5) to the monomer unit of the formula (6) is 95: 5 to 40:60, and the weight ratio is 90:10 to 60:40. More preferred. [0069] The monomer units other than those contained in the copolymer !, may! /, And formulas (5) and (6) include acrylic acid such as acrylic acid and methacrylic acid; acrylamide, Amide groups such as methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, epoxy groups such as glycidyl acrylate, glycidyl methacrylate, etc., jetylaminoethyl acrylate, jetylaminoethyl methacrylate, aminoethyl vinyl ether, etc. Monomers containing amino groups; other monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl butyl ether, vinyl chloride, vinyl acetate, butyl propionate, ethylene and the like.

[0070] The organic polymer (Α) having a reactive cage group may be used alone or in combination of two or more.

[0071] Specifically, a polyoxyalkylene polymer having a reactive cage group, a saturated hydrocarbon polymer having a reactive cage group, and a (meth) acrylic acid ester having a reactive cage group Copolymers, powerful group forces Organic polymers made by blending two or more types selected can also be used.

An organic polymer obtained by blending a saturated hydrocarbon polymer having a reactive cage group and a (meth) acrylic acid ester copolymer having a reactive cage group is disclosed in JP-A-1 16876.

Forces proposed in No. 4, Japanese Patent Laid-Open No. 2000-186176, and the like are not particularly limited thereto.

[0073] Further, as a method for producing an organic polymer obtained by blending a (meth) acrylic acid ester-based copolymer having a reactive cage functional group, other organic compounds having a reactive cage group can be used. A method of polymerizing a (meth) acrylic acid ester monomer in the presence of a polymer can be used. This production method is disclosed in JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, and the like. However, it is not limited to these.

[0074] Various compounds are used as the crosslinking regulator of the component (ii) in the present invention. As the component (ii) in the present invention, a compound that causes a reduction in the modulus of rubber properties after the reaction is used.

[0075] Examples of the component (ii) include diphenylsilanediol, diphenyldimethoxysila. (Bi) molecules such as dimethyldimethoxysilane, trimethylsilanol, triethylsilanol, triphenylsilanol, diphenylmethylsilanol, and phenyldimethylsilanol have one silicon atom. A silicon compound in which the total number of hydroxyl groups and hydrolyzable groups bonded to 1 or 2 is one (here, a hydrolyzable group is a group that can react with moisture to form a silanol group together with a silane atom. And (B-ii) the number of silicon atoms in the molecule is 2-20, such as 1, 3, 5-triphenyl-1, 3,5-trimethoxy-1, 5-dimethylsiloxane. Yes, the total number of hydroxyl groups and hydrolyzable groups bonded to any silicon atom in the molecule is 2 to 5, and each silicon atom has hydroxyl groups and hydrolyzable groups bonded to the same silicon atom. Counting silicon compounds is 0 or 1.

[0076] In the silicon compound of (B—i) or (B—ii), the group other than the hydroxyl group bonded to the silicon atom or the carohydrolyzable group includes an alkyl group having 1 to 20 carbon atoms and a carbon number. Examples include aryl groups having 5 to 20 carbon atoms and aralkyl groups having 6 to 20 carbon atoms.

[0077] Silicone compound (B-iii) represented by formula (1) is also preferable as a crosslinking regulator.

R ⁴ — NH— R ¹ — Si (R ² ) (R ³ ) (1)

z 3-z

(Where R ¹ is a branched or cyclic alkylene group, an arylene group, an alkali monolene group or an alcoholylalkylene group, and when R ¹ has 4 or more carbon atoms, these groups are! , Any of which may contain one or more oxygen atoms or (poly) sulfide bonds R ² is an alkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 20 carbon atoms R ³ is a C1 to C6 alkoxy group or a C3 to C5 ketoximate group R ⁴ is a hydrogen or hydrocarbon group, or is thermally bonded to itself. It is a group that forms an amine group containing a nitrogen atom, and z is 0 or 1. Note that an alkali monolene group is a divalent group in which one of the bonds is on the aryl group and the other is on the alkyl group. It refers to a hydrocarbon group. The alkaryl group is an aryl group having an alkyl group in which a bond is present on the aryl group. An alkaryl alkylene group is a divalent group in which an alkylene group is further bonded to an aryl group of an alkaryl group, and two bonds are present on different alkyl groups.

[0078] Specific examples of R ¹ include 1, 3-butylene, 1,2-butylene or 2,2-dimethyl-1, 3 Propylene, 3-methylbutylene, 3, 3-dimethylbutylene, 2-ethylhexylene

1,4-diethylenephenylene, 3-phenyl-1,3-propylene, 1,4-cyclohexylene, 1,4-diethylenecyclohexylene, and the like.

A preferred R ¹ group is a branched alkylene group having 4 to 8 carbon atoms.

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

[0081] Preferable! / ヽ The R ² group does not exist! ヽ (z = 0), or is a methyl group.

[0082] Specific examples of R ³ include methoxy, ethoxy, isopropoxy, n-propoxy, phenoxy

, 2-phenylethoxy, dimethylketoximo, methylethylketoximo, jetylketoximo and the like.

[0083] Preferred R ³ groups are methoxy and ethoxy.

[0084] Specific examples of R ⁴ include hydrogen, methyl, ethyl, 2-aminoethyl, propyl, 3-aminopropyl, butyl, cyclohexyl, phenol, methylphenol, 2-cyanoethyl, isopropoxy. A chill etc. are mentioned. When R ⁴ is a substituted hydrocarbon, acceptable substituents include sheared alkoxy and amino. Further, when exposed to temperatures of about 150 ° C. or higher during the reaction, R ⁴ may be a group that thermally deblocks to form an amine.

[0085] Preferred compounds as the compound of the formula (1) are N-ethyl-3-aminoisobutyltrimethoxysilane, N-ethyl-3-aminoisobutyldimethoxymethylsilane, 4 amino-3,3-dimethylbutyltrimethoxysilane, 4 Amino-3,3-dimethylbutyldimethoxymethylsilane, N-methyl-4amino-3, 3-dimethylbutyltrimethoxysilane, amino isopropoxytyltrimethoxysilane, aminoaminopropoxypropyltrimethoxysilane and the above methoxy group is ethoxy Or a mixture of ethoxy and methoxy groups.

[0086] The catalyst (C) in the present invention is a catalyst for the reaction of a reactive group of an organic polymer (A) having an average of 0.8 or more reactive cage groups in one molecule. Good!

[0087] Specific examples thereof include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and titanium tetraacetyl acetate; dibutyltin dilaurate, dibutyltin Maleate, Dibutinoles phthalate, Dibutyltin diotatate, Dibutinores dimethinolate, Dihexinoles dimethinole maleate, Dibutinoles dimethinore maleate, Dibutinoles dibutinore , Dibutinoles dioctinore maleate, dibutinole tin ditridecyl maleate, dibutyltin dibenzyl maleate, dibutyltin dicetate, dioctinoles jechinore maleate, dioctinoles Octinore maleate, dibutyltin dimethoxide, dibutyltin dinoyulphenoxide, dibutyrtin oxide, dibutyltin diacetylacetonate, dibutyltin diethylacetoacetate, reaction product of dibutyltin oxide and phthalate, etc. Suzui Divalent tin compounds such as tin octylate, tin naphthenate, tin stearate and tin tin versatate; aluminum triacetyl acetate, aluminum triacetyl acetate, diisopropoxy aluminum acetate Organoaluminum compounds such as acetoacetate; Zirconium compounds such as zirconium tetraacetylacetonate; Lead octylate; Butylamine, Octylamine, Dibutylamine, Monoethanolamine, Diethanolamine, Triethanolamine, Diethylenetriamine, triethylenetetramine, oleylamine, laurylamine, cyclohexylamine, benzylamine, jetylaminopropynoleamine, xylylenediamine, triethylenediamine, guanidine, diphenyl Noreguazine, 2, 4, 6 Tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2 ethyl-4-methylimidazole, 1,8 diazabicyclo (5, 4, 0) undecene-7 (DBU) , N, N-Jetylpropanediamine and other amine compounds, or salts of these amine compounds with carboxylic acids, etc .; excess polyamines and polybasic acids, resulting in low molecular weight polyamide resin; excess Product of reaction of polyamine with epoxy compound; silane coupling agent having amino group such as γ-aminopropyltrimethoxysilane, _Ν- (β-aminoethyl) _Ί -aminopropylmethyldimethoxysilane, etc. And known silanol condensation catalysts such as other acidic catalysts and basic catalysts. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is preferably about 0.01 to 20 parts by weight per 100 parts by weight of component (i). More preferred is about LO parts by weight. [0089] If the amount of the catalyst used is too small, the reaction rate becomes slow and it is difficult to proceed sufficiently. On the other hand, if the amount of the catalyst used is too large, local heat generation and foaming occur during the reaction, which makes it difficult to obtain a good composition, which is not preferable.

[0090] The (D) filler in the present invention is not limited to a specific filler. Specific examples include fumed silica, precipitated silica, anhydrous key acid, hydrous key acid and carbon black, calcium carbonate, magnesium carbonate, calcium oxide, calcium hydroxide, diatomaceous earth, calcined clay, clay and talc. Inorganic fillers, PVC powder, acrylic resin powder, organic fillers such as polyolefin powder; fibrous fillers such as asbestos, glass fibers and filaments, inorganic balloons such as shirasu balloon, glass nolane and saran balloon Organic balloons such as phenol balloons are exemplified, and one or more of these may be used. The filler is preferably used in an amount of 10 to 300 parts by weight, particularly 50 to 200 parts by weight, based on 100 parts by weight of component (A). If the amount is less than 10 parts by weight, the effect as a filler is difficult to be exhibited.

[0091] The composition of the present invention is blended with a crosslinking regulator (B) for the purpose of adjusting the gel fraction of the cured product. The gel fraction may be adjusted by increasing or decreasing the blending amount of the crosslinking regulator (B) or changing the type and amount of the catalyst (C). As a guideline for the adjustment, the gel fraction based on the total amount of (A), (B) and (C) in the cured product obtained by curing at normal temperature and humidity for 8 days is 20 weight. U, prefer to adjust to less than%. Preferably it is less than 10%.

[0092] A tackifier resin, a plasticizer, an adhesion promoter, a solvent, other additives, and the like can be added to the composition of the present invention as necessary.

[0093] Specific examples of tackifying resins that can be used in the composition of the present invention include styrene (co) polymers such as styrene, vinyl toluene, _α -methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof, Coumarone indene resin, coumarone resin mixed with naphthenic resin, phenolic resin, rosin etc. in coumarone resin, p-t-butylphenol acetylene resin, low polymerization degree and low softening point (60〜: LOO ° C) phenol formaldehyde resin, xylene phenol resin, xylene resin, terpene resin that improves adhesiveness and heat resistance as well as tackiness, phenolic resin such as terpene resin Terpene resin, synthetic polyterpene resin, aromatic hydrocarbon resin, aliphatic hydrocarbon resin, aliphatic cyclic hydrocarbon resin, hydrogenated hydrocarbon resin, etc. Resin, pentaerythritol ester of rosin or rosin, glycerol ester of rosin, hydrogenated carbine, highly hydrogenated wood resin, methyl ester of hydrogenated rosin, triethylene of hydrogenated rosin Glycol esters, pentaerythritol esters of hydrogenated rosin, polymerized rosin, glycerol esters of polymerized rosin, zinc oxalate, hardened rosin, and low molecular weight polystyrene. Other special preparations. These tackifier resins can be used alone or in combination of two or more. The amount of tackifying resin used is preferably 1 to 150 parts by weight per 100 parts by weight of component (A).

[0094] Specific examples of the plasticizer used in the composition of the present invention include, for example, dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, butyl phthalyl butyl dalicolate. Non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Polybutene, polybutadiene, non-reactive poly Hydrocarbon plasticizers such as isobutylene; alkyl sulfonic acid phenolic esters such as mesamol and mesamol II (manufactured by Bayer); epoxy plasticizers such as epoxidized soybean oil and epoxidized flax oil, alkyl arylsulfonamide Kind.

[0095] A polymer plasticizer can also be used. When a high-molecular plasticizer is used, the initial physical properties can be maintained over a long period of time compared to the case where a low-molecular plasticizer that is a plasticizer that does not contain a polymer component in the molecule is used. Specific examples of the polymer plasticizer include a bull polymer obtained by polymerizing vinyl monomers by various methods; polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol oleesterol. Esters of polyesters: Polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid, and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol A polyether polyol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like having a molecular weight of 500 or more, or 1000 or more Polyethers such as derivatives obtained by converting the hydroxyl groups of these polyether polyols to ester groups, ether groups, etc .; polystyrenes such as polystyrene and poly- _a- methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene acrylonitrile, polychloroprene, etc. The powers listed are not limited to these.

[0096] These plasticizers may be used alone or in combination of two or more.

[0097] The amount of plasticizer used is preferably 10 to 300 parts by weight per 100 parts by weight of component (A).

[0098] Specific examples of the adhesion-imparting agent include silane coupling agents, reactants of silane coupling agents, and compounds other than silane coupling agents. Specific examples of the silane coupling agent include y-isocyanate propyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-isocyanate propylmethyl jetoxysilane, and y isocyanate propylmethyldimethoxysilane. Isocyanate group-containing silanes such as: y-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ aminopropylmethyldimethoxysilane, γ-aminopropylmethyljetoxysilane, Ν— (2 —amino Ethyl) 3 Aminopropyltrimethoxysilane, Ν— (2 Aminoethyl) 3— Aminopropylmethyldimethoxysilane, Ν— (2 Aminoethyl) 3 Aminopropyltriethoxysilane, Ν- (2 Aminoethyl) 3 A Minopropylmethyl jetoxysilane, γ-uree Amino group-containing silanes such as dopropyltrimethoxysilane, ΝPheninore γ-Aminopropyltrimethoxysilane, ペン Penzinore γ-Aminopropyltrimethoxysilane, ΝVinolependenole y-aminopropyltriethoxysilane Γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyljetoxysilane-containing silanes such as γ-mercaptopropyltrimethoxysilane; Ύ-glycidoxypropyltri silane, y- Gurishidokishipu port pills _{triethoxysilane,} Ί - glycidoxypropyl methyldimethoxysilane, j8 (3, 4 epoxy cycloheteroalkyl Kishinore) E Chino Les trimethoxysilane, j8 (3, 4- epoxycyclohexyl) Echirutori Epoxy group-containing silane such as Tokishishiran; beta Karubokishechi Le triethoxysilane, / 3-carboxyanhydride Chez Chill Hue - bis (2-methoxyethoxy) silane, Nyu- (carboxymethyl) beta-aminoethyl one _I - § amino propyl trimethoxy Silane _{Carboxysilanes} such as vinyl trimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, _Ί-butyl unsaturated group-containing silanes such as acryloyloxypropylmethyltriethoxysilane; y —Halogen-containing silanes such as black propyltrimethoxysilane; isosilaneurate silanes such as tris (trimethoxysilyl) isocyanurate, and the like. Derivatives modified from these include amino-modified silyl polymers, silylaminoamino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilyl silicones, silyl polyesters, and the like. it can. The silane coupling agent used in the present invention is usually used in the range of 0.1 to 20 parts by weight per 100 parts by weight of component (A). In particular, it is preferably used in the range of 0.5 to 10 parts by weight.

[0099] The effect of the silane coupling agent added to the composition of the present invention is that various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, and mortar, vinyl chloride, acrylic When used for organic base materials such as polyester, polycarbonate, etc., it exhibits a remarkable effect of improving adhesion under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable. Specific examples other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resin, phenol resin, sulfur, alkyl titanates, and aromatic polyisocyanate. The adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesion-imparting agents, the adhesion to the adherend can be improved.

[0100] Examples of the solvent include non-reactive solvents such as hydrocarbons, acetate esters, alcohols, ethers, and ketones, and there are no particular limitations on such solvents.

[0101] Examples of other additives include an anti-sagging agent, a coloring agent, an antioxidant, a light stabilizer, and an ultraviolet absorber.

[0102] Specific examples of the sagging inhibitor include polyamide waxes; hydrogenated castor oil derivatives; metal stones such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents (thixotropic agents) may be used alone or in combination of two or more. The thixotropic agent is 0.1 to 20 weights per 100 weight parts of component (A). Used in part range.

[0103] Examples of the antioxidant (anti-aging agent) include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. JP-A-4-283259 is also described in JP-A-9-194731. Similarly, Tinuvin 622LD, Tinuvin 144;

CHIMASSORB944LD, CHIMASSORB119FL (above! /, The slippage is also special) ~ MARK LA- 57.MARK LA—62, MARK LA—67, MARK LA-63.MARK LA—68 (above any Asahi Denka Kogyo Co., Ltd.); Sanore LS-770, Sanore LS-765, Sanore LS-292, Sanore LS-2626, Sanol LS-114, Sanol LS-744 It is also possible to use a hindered amine light stabilizer prepared. The amount of the antioxidant used is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the component (A).

[0104] Examples of the light stabilizer include benzotriazole-based, hindered amine-based, and benzoate-based compounds. Particularly, hindered amine-based compounds are preferable. The amount of the light stabilizer used is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of component (A). Specific examples of the light stabilizer are also described in JP-A-9-194731.

[0105] Examples of the ultraviolet absorber include benzozoenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds. Particularly, benzotriazole-based compounds are preferable. The ultraviolet absorber is used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight per 100 parts by weight of component (A). It is preferable to use a phenol-based hindered phenolic acid inhibitor, a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in combination.

[0106] Various additive agents may be added to the composition of the present invention as needed for the purpose of adjusting the physical properties of the composition. Examples of such additives include, for example, adhesion improvers, storage stability improvers, flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxides. Decomposition agents, lubricants, pigments, foaming agents, solvents, fungicides, etc. can give. These various additives may be used alone or in combination of two or more. Specific examples other than the specific examples of the additives listed in the present specification include, for example, JP-B-469659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, 2 It is described in each publication of 001-72854.

[0107] In order to impart high elongation performance, a compound having an α, β-diol or a, γ-diol structure as disclosed in JP-A-11-080533 can also be added.

[0108] The production method of the composition of the present invention is not particularly limited. For example, the above components are blended and kneaded using a mixer, a roll, or a roll, etc., each component is dissolved using a solvent. A usual method such as mixing may be employed. In addition, this composition can be a one-component type or a two-component type, or a misaligned composition.

[0109] When the composition is of a one-component type, all the blended components are blended in advance, so that the blended components containing moisture are used after dehydrating and drying in advance, or by reducing the pressure during blending and kneading. It is preferable to dehydrate. When the composition is a two-component type, it is necessary to add a catalyst to the main component containing the organic polymer, so there is some moisture in the compounding agent! Although there is little concern about gelling, it is preferable to dehydrate and dry when long-term storage stability is required. As the dehydration and drying method, a heat drying method is preferable in the case of a solid substance such as a powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel or the like is preferable in the case of a liquid material. Alternatively, a small amount of isocyanate compound may be blended and the isocyanate group and water reacted to dehydrate. Lower alcohols such as methanol and ethanol in addition to powerful dehydration and drying methods; η-propyltrimethoxysilane, butyltrimethoxysilane, vinylmethyldimethoxysilane, γ mercaptopropylmethyldimethoxysilane, γ mercaptopropylmethyl jetoxysilane The storage stability is further improved by adding an alkoxysilane compound such as γ-glycidoxypropyltrimethoxysilane.

[0110] The amount of a dehydrating agent, particularly a key compound capable of reacting with water such as vinyltrimethoxysilane, is 0.1 to 20 parts by weight, preferably 0.5 to 100 parts by weight of component (ii). A range of 10 parts by weight is preferred.

Example [0111] The composition of the present invention will be described based on examples. EXAMPLES Hereinafter, the present invention will be specifically described with reference to synthesis examples and examples, but the present invention is not limited to these synthesis examples and examples.

[0112] (Synthesis Example 1)

A polyoxypropylene diol having a number average molecular weight of 2000 is used as an initiator and a polymetal cyanide complex catalyst is used to polymerize propylene oxide to produce a polymer having a number average molecular weight of 25,400 (polystyrene conversion value obtained from GPC). Oxypropylene diol was obtained. After adding 2.5 parts by weight of a 30% methanol solution of sodium methylate, devolatilization was performed at 130 ° C until no methanol was recovered. Then, after adding 3 parts by weight of allyl chloride and reacting for 5 hours, unreacted allyl chloride was removed by devolatilization under reduced pressure, and then purified with hexane and water, with an average of 2 in one molecule. Thus, an oxypropylene polymer (P1) containing an aryl terminal group was obtained.

[0113] (Synthesis Example 2)

Polymerization of propylene oxide using a polyoxypropylene diol having a number average molecular weight of 2000 as an initiator and a composite metal cyanide complex catalyst to give a number average molecular weight of 3 8000 (polystyrene conversion value obtained from GPC), molecular weight A polyoxypropylenediol with a distribution of 1.4 was obtained. After 2 parts by weight of a 30% methanol solution of sodium methylate was added, 1 devolatilization was performed at 30 ° C until no methanol was recovered. Then, 1.2 parts by weight of aryl chloride was added and reacted for 5 hours, and then unreacted aryl chloride was removed by devolatilization under reduced pressure, followed by purification with hexane and water, and an average of 2 per molecule. An oxypropylene polymer (P2) containing a number of aryl end groups was obtained.

[0114] (Synthesis Example 3)

Polymerization of propylene oxide using a polyoxypropylene diol having a number average molecular weight of 2000 as an initiator and a composite metal cyanide complex catalyst, a number average molecular weight of 15000 (polystyrene conversion value obtained from GPC), molecular weight Distribution 1. Polyoxypropylene diol of 1 was obtained. After adding 4.2 parts by weight of a 30% methanol solution of sodium methylate, devolatilization was performed at 130 ° C. until no methanol was recovered. Next, add 8 parts by weight of the aryl chloride, react for 5 hours, and remove the unreacted aryl chloride under reduced pressure. After removal by volatilization, purification with hexane and water yielded an oxypropylene polymer (P3) containing an average of two aryl end groups in one molecule.

[0115] (Synthesis Example 4)

Dimethoxymethylsilane 0.4 mol was reacted with 1 mol of P1 allyl group obtained in Synthesis Example 1 in the presence of salt and platinum acid, and an oxypropylene polymer having a dimethoxymethylsilyl group at the molecular end (P4 )

[0116] (Synthesis Example 5)

0.6 mol of dimethoxymethylsilane is reacted in the presence of salt and platinum acid with respect to 1 mol of P1 aryl group obtained in Synthesis Example 1 to give an oxypropylene polymer having a dimethoxymethylsilyl group at the molecular end (P5 )

[0117] (Synthesis Example 6)

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

[0118] (Synthesis Example 7)

Dimethoxymethylsilane 0.65 mol was reacted in the presence of chloroplatinic acid with respect to 1 mol of P2 allyl group obtained in Synthesis Example 2, and an oxypropylene polymer having a dimethoxymethylsilyl group at the molecular end (P7) Got.

[Synthesis Example 8]

0.4 mol of dimethoxymethylsilane is reacted with 1 mol of P3 aryl group obtained in Synthesis Example 3 in the presence of salt and platinum acid, and an oxypropylene polymer having a dimethoxymethylsilyl group at the molecular end (P8 )

[0120] (Synthesis Example 9)

Polymerization of propylene oxide using a polyoxypropylene diol having a number average molecular weight of 2000 as an initiator and a composite metal cyanide complex catalyst results in a polymer having a number average molecular weight of 25400 (polystyrene conversion value obtained from GPC). Oxypropylene diol was obtained. Add 0.4 mole of γ-isocyanate-pyrutrimethoxysilane to 1 mole of hydroxyl group of the resulting polypropylene glycol to perform urethane reaction, and add trimethoxy at the molecular end. An oxypropylene polymer (P9) having a silyl group was obtained.

[0121] Table 1 shows a summary of the polymers obtained in Synthesis Examples 4 to 9. Table 2 shows the measurement results of the gel fraction.

[0122] [Table 1]

[0123] [Table 2]

Unit: parts by weight

[0124] [Method of measuring silylation rate — Method of measuring silylation rate (%) determined by NMR)]

• Use the integral value of the polymer main chain peak as an internal standard, and calculate from the integral reduction value of the aryl group peak before and after the silylation reaction.

[0125] [Method of measuring gel fraction]

'Polymer, crosslinking modifier, catalyst and water are mixed in the specified amount shown in the table, defoamed with a centrifuge (3,000rpm, lmin), and then poured into a mold (width 14cm x height 7cm x height 3mm) Come on. After curing at 23 ° C for 8 days, cut about lOOmg from the cured sheet and place in a wire mesh. Immerse it in acetone at 23 ° C for 1 day, pull it up, lightly wash it with acetone, and dry it in a 50 ° C oven for about 2 hours. Weight change force before and after immersion Calculate gel fraction.

[0126] (Example 1)

An organic polymer having an average of 0.8 or more reactive cage groups per molecule (A) component and 100 parts by weight of P4 obtained in Synthesis Example 4, 1 part by weight of diphenyldimethoxysilane (hereinafter referred to as B-1) as the crosslinking regulator (B), and U-220 as the catalyst for component (C) 1 part by weight (dibutyltin diacetylacetonate), 120 parts by weight of Ultrapflex (glue calcium carbonate, Specialty Minerals) as filler (D), and butyltrimethoxysilane (A-171, Nippon 2 parts by weight) were sufficiently mixed to prepare a one-part composition, filled in a cartridge, and subjected to the following test.

[0127] (Adhesion test method)

Produced a T-type peel test piece with an adhesive layer thickness of lmm. After curing for 7 days at 23 ° C, a T-type peel test was conducted at a test speed of 50 mmZmin.

[0128] (Hard-bonding substrate)

SBR (styrene butadiene rubber) substrate;

Engineering Test Service Co., Ltd., 25 X 100 X 3mm

EPDM substrate;

Engineering Test Service Co., Ltd., 25 X 100 X 3mm

TPO substrate;

Carlisle Waterproof membrane sample (thermoplastic polyolefin base material, base material based on polypropylene resin)

25 X 100 X 1.5 mm

(Example 2)

A composition was prepared in the same manner as in Example 1, except that N-ethyl-3-aminoisoptyltrimethoxysilane (hereinafter referred to as B-2) was used as the crosslinking regulator (B). went.

[Example 3]

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

[0130] (Example 4)

A composition was prepared in the same manner as in Example 1 except that 100 parts by weight of P7 obtained in Synthesis Example 7 was used as component (A) and 5 parts by weight of B-2 was used. Went. [0131] (Example 5)

Use 100 parts by weight of P8 obtained in Synthesis Example 8 as component (A) and 1.5 parts by weight of B-1

A composition was prepared in the same manner as in Example 1 except that 150 parts by weight of component (D) was used, and the same evaluation was performed.

[0132] (Example 6)

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

[0133] (Comparative Example 1)

A composition was prepared in the same manner as in Example 1 except that the component (B) was not used, and the same evaluation was performed.

[0134] (Comparative Example 2)

A composition was prepared in the same manner as in Example 1 except that the component (D) was not used, and the same evaluation was performed.

[0135] (Comparative Example 3)

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

[0136] The results are summarized in Tables 3 and 4.

[0137] [Table 3]

Unit: parts by weight

(B-1); Diphenyldimethyoxysilane

(B- 2); N-ethyl 3-aminoaminoptyltrimethoxysilane

[0138] [Table 4]

(Unit: kgf / 25

[0139] As shown in Table 4, it can be seen that Examples 1 to 6 have better adhesion to difficult-to-adhere substrates than Comparative Examples 1 to 3.

Claims

The scope of the claims

[1] Reaction comprising an organic polymer (A) having an average of 0.8 or more reactive cage groups in one molecule, a crosslinking regulator (B), a catalyst (C) and a filler (D) Rosin composition.

[2] The reactive resin composition according to claim 1, wherein the average number of reactive groups in the organic polymer (A) is 0.8 to 1.4 per molecule.

[3] Crosslinking regulator (B)

(B-iii) Silicone compound of the following formula (1)

R ⁴ — NH— R ¹ — Si (R ² ) (R ³ ) (1)

z 3-z

(Where R ¹ is a branched or cyclic alkylene group, an arylene group, an alkali monolene group or an alcoholylalkylene group, and when R ¹ has 4 or more carbon atoms, these groups are! , Any of which may contain one or more oxygen atoms or (poly) sulfide bonds R ² is an alkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 20 carbon atoms R ³ is a C1 to C6 alkoxy group or a C3 to C5 ketoximate group R ⁴ is a hydrogen or hydrocarbon group, or is thermally bonded to itself. 3. The reactive resin composition according to claim 1, which is a group that forms an amine group containing a nitrogen atom, and z is 0 or 1.

[4] The reactive resin composition according to any one of claims 1 to 3, comprising 10 to 300 parts by weight of a filler (D) with respect to 100 parts by weight of the organic polymer (A).

[5] The main chain skeleton of the organic polymer (A) is an alkylene oxide polymer.

V, Reactive rosin composition according to any of the above.

[6] The reactive resin composition according to any one of claims 1 to 5, wherein the organic polymer (A) has a number average molecular weight of 10,000 to 10,000.

[7] The cured product obtained by curing for 8 days at room temperature and humidity has a gel fraction of less than 20% by weight based on the total amount of components (A), (B) and (C). Claim 1 adjusted to be

The reactive rosin composition according to any one of -6.

[8] An adhesive comprising the reactive resin composition according to any one of claims 1 to 7.

9. The adhesive according to claim 8, which is used for a hardly adhesive substrate.