JPS59170139A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition of long pot-life at room temperature capable of rapidly curing on heating to high temperatures, by incorporating a polyoxyalkylene having hydrolyzable silicon group with a curing catalyst consisting of an organic acid phosphoric acid compound and amine. CONSTITUTION:The objective composition can be obtained by incorporating (A) 100pts.wt. of a polyoxyalkylene having in one molecule at least one hydrolyzable silicon group with (B) 0.1-10pts.wt. of a curing catalyst consisting of (1) a P-OH bond-carrying organic acid phosphoric acid compound of formula I , II, III, or IV (R1, and R2 are each organic residue; n is zero or 1; x and y are each zero, 1, or 2; x+y is 1 or 2) and (2) an amine of secondary or tertiary type having bydrolyzable silicon group. The component (A) is such that the main chain consists essentially of 1-4C oxyalkylene polymer, with a molecular weight 3,000-15,000 and hydrolyzable silicon group(s) at the molecular end(s).

Description

DETAILED DESCRIPTION OF THE INVENTION Polyoxyalkylene having a degradable silicon group and P-O
The present invention relates to a novel thermosetting resin composition containing as an active ingredient a curing catalyst containing an organic acidic phosphoric acid compound having an H bond and an amine compound.

More specifically, the present invention relates to a thermosetting resin composition that has a long pot life at around room temperature and can be rapidly cured by being heated to a high temperature.

The present inventors have previously discovered that compositions containing polyoxyalkylene as an active ingredient having at least one hydrolyzable silicon group in one molecule can be used as sealants, coating materials, casting materials, foam materials, adhesives, etc. It has been found that it is useful for adhesives, pressure-sensitive adhesives, etc. However, since the curing characteristics of polyoxyalkylene having a hydrolyzable silicon group are greatly affected by the type of curing catalyst used, it is necessary to select a curing catalyst that is suitable for the purpose and use of the cured product. For example, when polyoxyalkylene having a hydrolyzable silicon group is used as a pressure-sensitive adhesive, it is difficult to balance pot life and curing speed with conventionally known catalyst systems, which poses a practical problem.

In other words, polyoxyalkylene with hydrolyzable silicon groups is stable for a long time without the addition of a curing catalyst, and does not thicken or gel. However, once a curing catalyst is added, the polyoxyalkylene remains in the polymer and formulation even at room temperature. Trace amounts of water contained in the adhesive can cause the hydrolyzable silicon groups in the polymer molecules to react, increasing the viscosity of the adhesive formulation and causing it to gel before being applied to the substrate.

As a result, it becomes difficult to apply the adhesive to the support,
Further, there is a problem that not only the coated surface becomes uneven due to the gelled product, but also the adhesive properties become unstable.

To solve the above problem, the pot life can be made to a desired length by reducing the amount of curing catalyst blended, but in that case, even if heated to a high temperature, a sufficient curing rate cannot be changed. On the other hand, if the amount of curing catalyst compounded is increased, curing will occur quickly under high temperature conditions, but the pot life will be shortened, which is a major obstacle in practical use.

In order to avoid such problems, a method is employed in which a curing catalyst or its solution is applied onto a support in advance and then an adhesive that does not contain the catalyst is applied, or an adhesive that does not contain a curing catalyst is applied onto the support. A method of later applying the catalyst or its solution separately by spraying or the like may be considered, but this method has the disadvantage of complicating the process.

In view of the above-mentioned circumstances, the present inventors have conducted intensive research and have found that the above-mentioned problem can be solved by using a specific catalyst system as a curing catalyst, and have completed the present invention.

That is, (A) polyoxyalkylene having at least one hydrolyzable silicon group in one molecule and (E) P-o
A thermosetting resin composition containing, as an active ingredient, a curing catalyst containing an organic acidic phosphoric acid compound having an n-bond and an amine compound has a sufficiently long pot life at around room temperature, and is rapidly cured by being heated to a high temperature. We have discovered that the material can be hardened to a certain extent, which is an extremely useful property from a practical standpoint.

Conventionally, when an organic acidic phosphate ester is used alone as a curing catalyst, the curability of the composition is improved, but the pot life is shortened, and when an amine compound is used alone as a curing catalyst, the pot life of the composition is shortened. However, it is known that the curing rate decreases significantly, and in any case, it is difficult to adjust the balance between pot life and curing rate by adjusting the amount of a single catalyst used.

The present inventors found that when an amine compound is gradually added to an organic acidic phosphate as a curing catalyst, the amine content in the curing catalyst increases, the curing speed of the composition at room temperature decreases, and the pot life becomes longer. The present invention was completed based on the discovery of the fact that the material cures more quickly under high-temperature conditions.

As the polyoxyalkylene having a hydrolyzable silicon group used in the present invention, for example, Japanese Patent Publication No. 45-3631
Publication No. 9, Publication No. 46-12154, Publication No. 46-307
Publication No. 11, Publication No. 4B-56960, Japanese Unexamined Patent Publication No. 1983-
Compounds and structural formulas (
1) Obtained by an addition reaction using a platinum-based compound as a catalyst between a polyoxyalkylene having an olefin group at the end represented by the formula (1) and a silicon hydride compound represented by the structural formula (2): Structural formula (3): Polyoxyalkylene having a hydrolyzable silicon group or silanol group at the end [In formulas (1), (2) and (3) above, R3 is H- or the same or different divalent organic group having 1 to 20 carbon atoms, R4 is H- or the same or different monovalent organic group having 1 to 20 carbon atoms, R5
represents the same or different monovalent hydrocarbon group, triorganosiloxy group and/or silanol group, or the same or different hydrolyzable functional group, a is 0 or 1,
b is 0.1 or 2, C is 0.1.2 or 3, and 1≦b −1−o≦4, and m is an integer of 0 to 18].

In formulas (2) and (3), R5 has 1 to 1 carbon atoms.
selected from 20 same or different monovalent hydrocarbon groups, such as alkyl groups such as methyl and ethyl, cycloalkyl groups such as cyclohexylnato, aryl groups such as phenyl groups, and aralkyl/l' groups such as benzyl groups, Furthermore, the formula: % formula % (in the formula, R5 is the same or different 1 having 1 to 20 carbon atoms)
It also includes a triorganosiloxy group represented by (representing a valent hydrocarbon group). Also, in equations (2) and (3),
X represents a sila/-yl group or a different or the same type of hydrolyzable functional group, and examples of the hydrolyzable functional group include a halogen group, a hydride group, an alkoxy group, an acyloxy group, a ketoximate group, and an amide group. group, amide group,
Examples include aminooxy group, mercapto group, and alkenyloxy group. Specifically, the silicon hydride compound represented by the formula (2) includes halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, trimethylsiloxydichlorosilanato, trimethoxysilane, triethoxysilane, Methyldimethoxysilane, phenyldimethoxysilane, i, 3.3.5゜5
, 7. Alkoxysilanes such as 7-hebutamethyl-1,1-dimethoxytetrasiloxane, acyloxysilanes such as methyldiacetoxysilane and trimethylsiloxymethylacetoxysilane - bis(dimethylketoximate)methylsilane 1bis Ketoximate silanes such as (cyclohexylketoximate) methylsilane, bis(diethylketoximate)trimethylsiloxysilane, hydrocarbons such as dimethylsilane, trimethylsiloxymethylsilane, 1,1-dimethyl-2,2-dimethyldisiloxane, Examples include, but are not limited to, silanes and alkenyloxysilanes such as methyltri(impropenyloxy)silane.

In the addition reaction, after the silicon hydride compound of formula (2) is reacted with the polyoxyalkylene having an olefin group of formula (1), some or all of the X groups are further reacted with other hydrolyzable groups. Converted into a functional group or hydroxyl group.

For example, when the X group is a halogen group or a hydride group, it is preferable to use it after converting it into an alkoxy group, an acyloxy group, an aminooxy group, an alkenyloxy group, a hydroxyl group, or the like.

In formulas (1) and (3), R4 is H- or a monovalent organic group having 1 to 20 carbon atoms, preferably H- or a hydrocarbon group, and particularly preferably R-.

R3 is the same or different type of divalent organic group having 1 to 20 carbon atoms, preferably a hydrocarbon group and a hydrocarbon group containing an ether bond, an ester bond, a urethane bond, or a carbonate bond, particularly a methylene group. is preferred. The specific method for producing polyoxyalkylene having an olefin group represented by the formula (1) is the method already disclosed by the present inventors in JP-A No. 54-6097, or the method using ethylene oxide, propylene oxide, etc. It can be produced by a method in which an olefin group-containing epoxy compound such as allyl glycidyl ether is added to copolymerize an epoxy compound such as allyl glycidyl ether, thereby introducing an olefin group into the side chain.

The main chain of the polyoxyalkylene used in the present invention essentially has the formula: It is most effective when certain chemically bonded repeating units are shown. Specifically, R7 is 0H2-2-0'H20H
2-1 -0HOH2-1-0HGH2-10-0H2- and OH3 -OH20H20H20H2-, etc., which may consist of only one type of repeating unit, or may consist of two or more types of repeating units. Oxyalkylenes are also usefully used. Particularly preferred is OH3-0HOH2-.

Polyoxyalkylene having a molecular weight of 1,500 to 1,000 can be effectively used, but preferably 3,000 to i
One having a molecular weight of 500 is preferable.

Such polyoxyalkylene is disclosed in Japanese Unexamined Patent Application Publication No. 55-12
No. 9247, No. 54-6097, No. 55-8
No. 2123, No. 55-131021, No. 55
The method disclosed in Japanese Patent No. 131022, No. 55-157129, and No. 55-135135 can also be used.

These polyoxyalkylenes having a hydrolyzable silicon group or silanol group at the molecular terminal and/or side chain can be used alone or in combination of two or more. In addition, compositions obtained by polymerizing polymerizable monomers in a mixture or a solution of one or more types of polymers having hydrolyzable silicon groups or silanol groups in the molecules, and It is also possible to use simple mixtures of polymers with hydrolyzable silicon or silanol groups and other non-silane or silane polymers.

The non-silane or silane polymers include acrylic ester polymers, acrylic ester copolymers, which have or do not have a functional silyl group at the end of the side chain in the molecule; alkyl vinyl ether polymer,
Examples include vinyl polymers such as alkyl vinyl ether copolymers and ethylene-vinyl acetate copolymers, polyesters, diene polymers, and polysiloxanes.

The curing catalyst used in the present invention is a mixture of an organic acidic phosphoric acid compound and an amine compound.

The organic acidic phosphoric acid compound has the general formula: % formula %) [wherein R1 and R2 are organic residues, n is 0 or 1,
x and y are oll or 2, and X and y are 1 or 2].

Examples of the phosphoric acid compound include (OH30J2FOHX(OH30)P (OH)2,
(02H50), 2P OH.

00 0 0 00
00 0 Q 0 0゜0 0゜0 ((OH20H) (OHOH)OH20)2 poH
J: (OH20H) (OHOH)OH20)P-As the phosphorous acid compound, even &yo (OH30)2P
OH% 0H30P (OH)2, (02H50)2P
OH,021(50F'(O)O2,[(OHsu20
HO)2POH,' (OHsu20HOP (O town, (
04HgO)2PO)I.

O4Hg0P, (O glare, (043H470)2POI(
,0BH170P (O smell 2, (a 10H210)2
P 0H1010H210P (OR)2- (O13
H270)2POH-013H270P (O)O2,
(04Hg002H40)2POH,O4Hg002H
40P--(OR)2, (OIOH20H20)2P
OH,0IOH20H20P(O)ri2, there is no particular restriction on the number of amine compounds used in the present invention. grade amine,
Secondary amines such as diethylamine, dibutylamine, bipeinodine, piperazine, jetanolamine, triethylamine, tributylamine, N,N-dimethylhexylamine, N,N-dimethyldecylamine, HlN-
Tertiary amines such as dimethyldodecylamine, N,N-dimethylbenzylamine, N,N,N,N-tetramethyl-1,6-hexanediamine, triethylenediamine, triethanolamine, pyridine, diethylenetriamine, triethylenetetramine , polyfunctional amines containing primary and secondary amines such as tetraethylenepentamine, adducts of primary and secondary amines with epoxy compounds, γ-aminopropyltrimethoxycidine, γ-amino Propyltriethoxysilane, N-β-aminoethyl-r-aminopropyltrimethoxysilane,
Reaction product of γ-amino/propyltrimethoxysilane and r-glycidoxypropyltrimethoxysilane, reaction product of γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane, N-β Examples include a reaction product of -aminoethyl-r-aminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

The amount of the curing catalyst formed by mixing the organic acidic phosphoric acid compound and the amine compound is 0.01 to 20 parts per 100 parts (parts by weight, the same applies hereinafter) of the hydrolyzable silicon group-containing polyoxyalkylene. , preferably 0.1 to 10 parts.

It is thought that when an organic acidic phosphoric acid compound and an amine compound are mixed at room temperature, heat is generated, and a salt consisting of equivalent amounts of the organic acidic phosphoric acid compound and the amine compound is formed. Therefore, the organic acidic phosphoric acid compound (A) and the amine compound (B)
The blending ratio is equivalent ratio (B) / (A) of 0.05 to 2.
0, preferably in the range of 0.1 to 10. Applicable amount ratio (
If B) / (A) is less than 0.05, the curing properties of the organic acidic phosphoric acid compound cannot be improved, and the composition will harden rapidly at around room temperature, and if it exceeds 20, the curing properties of the composition will decrease significantly. , bleeding of amine compounds tends to occur.

In other words, the present invention is characterized by three types of catalytically active species: an organic acidic phosphoric acid compound that is highly curable at room temperature, a salt consisting of an organic acidic phosphoric acid compound and an amine compound that is highly curable when heated at 60° The proportion of the amine compound with low curability is determined by the above equivalent ratio (B) / (A)
The curing characteristics of the hydrolyzable silicon group-containing polyoxyalkylene can be arbitrarily set depending on the intended use.

The curing catalyst can be added by adding a mixture of a predetermined amount of an organic acidic phosphoric acid compound and an amine compound to the hydrolyzable silicon group-containing polyoxyalkylene, or by adding the organic fermentable phosphoric acid compound and the amine compound separately. It's okay.

The composition of the present invention can also be used by mixing the hydrolyzable silicon-based polyoxyalkylene and the curing catalyst immediately before use (two-component type). It is also possible to store the product without contamination and use it as is (one-liquid type).

In the present invention, in addition to the curing catalyst, additives such as fillers, plasticizers, anti-aging agents, colorants, tackifying resins, adhesion promoters, organic solvents, and the like may be added as necessary.

The compositions of the present invention can be modified by incorporating various fillers. Fillers include reinforcing fillers such as silica, precipitated silica, anhydrous silicic acid, hydrated silicic acid and carbon black, calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite. Fillers such as organic bentonite, ferric oxide, zinc oxide, activated zinc white, hydrogenated castor oil and shirasu balloons, etc., fibrous fillers such as asbestos, glass fibers and filaments can be used. If you want to obtain a cured product with high strength by using these fillers,
Mainly: Thumb silica, precipitated silica, anhydrous silicic acid, hydrated silicic acid, carbon black, surface-treated fine calcium carbonate,
Favorable results can be obtained by using one or more fillers selected from calcined clay, clay, activated zinc white, etc. in an amount of 1 to 100 parts per 100 parts of hydrolyzable silicon group-containing polyoxyalkylene. . In addition, if you want to obtain a cured product with low strength and high elongation, you can use one or two types selected from titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon. If the above fillers are used in the range of 5 to 200 parts per 100 parts of hydrolyzable silicon group-containing polyoxyalkylene, favorable results can be obtained.In the present invention, when a plasticizer is used in combination with a filler, the cured product It is more effective because it can increase the elongation of the material and mix a large amount of filler. Such plasticizers include common (commonly used phthalate esters such as dioctyl phthalate, diptylphthalate, butylbenzyl phthalate, etc., dioctyl adipate, isodecyl cono-monolyphosphate, and Aliphatic dibasic acid esters such as dibutyl sinate, glycol esters such as diethylene glycol dibenzoate, pentaerythritol ester, etc., aliphatic esters such as butyl oleate phosphoric acid esters such as tricresyl phosphate, trioctyl monomonoate, octyldiphenyl phosphate, etc., epoxy plasticizers such as epoxidized soybean oil, benzyl epoxy stearate, etc., chlorinated paraffins, etc. A single plasticizer or two or more plasticizers can be used optionally. The amount of plasticizer used is 0 to 100 parts per 100 parts of hydrolyzable silicon group-containing polyoxyalkylene.
Favorable results can be obtained if used within the range of 50%.

A tackifying resin may optionally further be used in the composition of the invention. Particularly when the composition of the present invention is used as a pressure-sensitive adhesive, good results can be obtained by incorporating a tackifier resin in order to improve the adhesive properties. As tackifier resins used for such purposes, rosin esters, terpene-phenol resins, phenol resins, xylene resins, etc. give particularly favorable results in terms of compatibility.

The amount of the tackifying resin used is 10 to 140 parts, preferably 20 to 120 parts, based on 100 parts of the polyoxyalkylene used. The organic solvent used in the present invention includes aliphatic hydrocarbons. , aromatic hydrocarbons, /・
logenated hydrocarbons, alcohols, ketones, esters, ethers, alcohol esters, ketone alcohols, ether alcohols, ketone ethers,
Examples include ketone esters and ester ethers.

Furthermore, when the solvent contains an alkyl alcohol and/or a hydrolyzable ester, the stability of the one-wave composition can be improved.

As such alkyl alcohol, alcohols having alkyl carbon atoms of 1 to 10 are preferable, and examples include methyl alcohol, ethyl alcohol, n-propyl alcohol,
Isopropyl alcohol, nibutyl alcohol, isobutyl alcohol-A/XsθC-butyl alcohol, te
Examples include rt-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexyl alcohol, octyl alcohol, and cellosolve.

Examples of the hydrolyzable ester include trialkyl orthoformates such as trimethyl orthoformate, triethyl orthoformate, triptevir orthoformate, and tributyl orthoformate, tetramethyl orthosilicate, tetraethyl orthosilicate,
Tetraalkyl orthosilicate such as tetrapropyl orthosilicate, tetrabutyl orthosilicate, and ethylsilicate 401 Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrisilicate Methoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane,
γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-amineethyl-r
Formula of -aminopropyltrimethoxysilane etc.: %Formula% (wherein, X is a hydrolyzable group, R8 is a monovalent organic group containing or not containing a functional group, t is an integer from 1 to 4,
Hydrolyzable silicon compounds represented by (preferably 3 or 4) and their partial hydrolysates are used.

The amount of the organic solvent varies depending on the molecular weight or composition of the hydrolyzable silicon group-containing polyoxyalkylene, and is used in accordance with the practically required concentration or viscosity of the composition. Furthermore, by adding a silane coupling agent or a nitrogen-containing compound having at least one silicon group bonded to a hydrolyzable group in one molecule, such as a silane coupling agent or a reactant thereof, to the composition of the present invention. It is possible to measure the improvement of the adhesion of objects.

The composition of the present invention has a long pot life at around room temperature, and hardens in a short time at high temperatures, so it is particularly useful as a reaction-curing pressure-sensitive adhesive. In other words, the composition of the present invention has the advantage of being free from the constraints of having to use it up immediately after being prepared, as there is no risk of thickening or gelling during storage for a long period of time. Even when applying the composition, there is no risk of thickening in a short period of time, so the workability is not impaired in any way.

In addition, after application, the reaction progresses quickly due to moisture in the air or moisture intentionally imparted with steam, etc., and also by adding normal heat treatment, resulting in good quality silane-reactive pressure-sensitive adhesive tapes. You can wander around.

Supports used in the present invention include kraft paper, Japanese paper, soft cloth, cotton cloth, cellophane, soft vinyl chloride film, polypropylene film, polyethylene film, polyester film, untreated, surface-treated paper such as corona treatment or braimer treatment, Conventionally used materials such as glass cloth are widely used, and are cut into tapes, sheets, labels, etc. depending on the purpose and use. Note that the tapes referred to in the present invention include tapes, sheets, and labels.

Hereinafter, the present invention will be explained in more detail with reference to Reference Examples, Examples, and Comparative Examples; however, the present invention is limited only to these Examples.

Reference Example 1 Polypropylene oxide (using 90% by weight of polypropylene glycol and 10% by weight of polypropylene trio-/L/L as starting materials) having an average molecular fjk of 9000 and containing allyl ether groups at 96% of all terminals. 9009 (manufactured) was placed in a pressure-resistant reaction vessel equipped with a stirrer.

01 Step 3 Add 20 ml of a silicon hydride compound having the structure H-51(OCH3)2, and then add a catalyst solution of chloroplatinic acid (H2Pt
8.99 of O16.6H20, isobrohydral alcohol-3mA and tetrahydrofuran 16 parts 1m/! After adding 0.34ml of the solution dissolved in the mixture of
The reaction was carried out at C for 6 hours. It was confirmed by Engineering R Spec F that the polypropylene oxide having (OH30)2-8i -0H20H20H20- groups at the terminals was changed.

Reference Example 2 A polypropylene oxide having a terminal (OH30)3Si-0H20H2GH20- group was obtained in the same manner as in Reference Example 1, except that trimethoxysilane 189 was used instead of methyldimethoxysilane.

Example 3 98 parts of butyl acrylate, 2 parts of trimethoxysilylpropyl methacrylate, 150 parts of toluene, and 5 parts of azobisisobutyronitrile were charged into a reaction vessel.
The reaction was carried out at 110°a for 5 hours with stirring under a nitrogen atmosphere. The obtained copolymer solution had a solid content concentration of 39.
6%, and the viscosity was approximately 70 poise (20°0).

Reference Example 4 100 parts of the hydrolyzable silicon group-containing polyoxyalkylene obtained in Reference Example 1 was placed in a reaction vessel, and the temperature was raised to 110°0 while stirring in a nitrogen atmosphere.

A mixed solution of 95 parts of butyl acrylate/I/1 and 5 parts of azobisisobutyronitrile was added dropwise to this over 6 hours.The viscosity gradually increased, but after stirring these for another 2 hours, A viscous, almost transparent liquid was obtained.

Reference Example 5 Dioctyl phosphate (D'OF) was used as the organic acidic phosphoric acid compound (A), and piperidine (PP), laurylamine (LA), and N,N were used as the amine compound (B).
- Select dimethyldodecylamine (MDA) and mix both at room temperature at the equivalent ratio (B)/(A) shown in Table 1, then dilute with toluene to make a 20% by weight solution of (A). A curing catalyst was prepared.

Examples 1 to 6 To the hydrolyzable silicon group-containing polyoxyalkylene obtained in Reference Example 1 (1oog), 1oop of terpene phenol resin (ys Polystar 'r-'N5, manufactured by Cheap Oil) and toluene 509 were added and uniformly dissolved. A solution with a viscosity of about 50 voids (20°C) was obtained. Then, the curing catalyst prepared in Reference Example 5 was added in an amount such that 3 g of DOP of the catalyst was added. The time from the time of addition of the curing catalyst until the length of the thread becomes 1 part cm or more when the composition to which the curing catalyst has been added is left standing in an open state at room temperature and the surface of the composition is pulled up with a spatula. The pot life was measured by 1. The pot life was determined by allowing the pot to stand still in a sealed state at room temperature, and the storage stability was determined by measuring the time from the time of addition of the curing catalyst until the pot became unusable due to thickening. The obtained composition was applied onto a 25 μm thick polyester film using a coater so that the glue thickness after drying was 40 μm, and then the composition was dried and cured using a hot air dryer at 120°O. Curability was measured by measuring time. The dry cure of the composition was determined by touching the surface of the composition with a finger. Furthermore, the pressure-sensitive adhesive film prepared using the obtained composition was attached to a stainless steel adherend, left at 23°0 for 2 hours, and then the tensile force when peeled at 180°0 in 7 minutes at a tensile speed of 300 mm was determined. The adhesion was measured by measuring. The results are shown in Table 1.

Example 7 To the hydrolyzable silicon group-containing polyoxyalkylene 1002 obtained in Reference Example 2, 100 g of rosin ester resin (Pencel A1 manufactured by Arakawa Chemical Co., Ltd.) and 50 g of toluene were added and uniformly dissolved to give a viscosity of about 40 bois (20° A solution of C) was obtained. Next, the curing catalyst prepared in Reference Example 5 was adjusted to the DOP of the catalyst.
was added in an amount such that 3 g was added, and the pot life, storage stability, curing property, and adhesive strength were measured using the same bacterial species as Examples 1 to 6. The results are shown in Table 1.

Example 8 The acrylic acid copolymer solution 1009 obtained in Reference Example 3 was mixed with the hydrolyzable silicon group-containing polyoxyalkylene 1009 obtained in Reference Example 1 and the terpene 7 ester resin (ys Polystar T-100, cheap crude oil (6 ) was added and dissolved uniformly, and then the curing catalyst prepared in Reference Example 5 was added so that the DOP of the catalyst was 31i+, and the pot life and storage stability were determined in the same manner as in Examples 1 to 6. The hardness, curability and adhesive strength were measured.The results are shown in Table 1.

Example 9 The curing catalyst prepared in Reference Example 5 was added to the liquid obtained in Reference Example 4 in an amount such that the DOP of the catalyst was 3 parts per 100 parts of hydrolyzable silicon group-containing polyoxyalkylene. Pot life, storage stability, curability and adhesive strength were measured in the same manner as in Examples 1-6. The results are shown in Table 1.

Comparative Examples 1 to 5 In Examples 1 to B, instead of the curing catalyst prepared in Reference Example 5, DOP was used as the organic acidic phosphoric acid compound (A), and PP, LA, and MDA were used as the amine compounds (B), respectively. Examples 1 to 6 except that the amounts shown in Table 1 were used.
A composition was prepared in the same manner as above, and the pot life, storage stability, curability, and adhesive strength were measured. The results are shown in Table 1.

Procedural official document (spontaneous) June 15, 1980 Commissioner of the Patent Office Kazuo Wakasugi 1. Indication of the case 1988 Patent Application No. 46513 2. Name of the invention Thermosetting resin composition 3. Person making the amendment Relationship to the incident Patent application Person 3-2-4 Nakanoshima, Kita-ku, Osaka Name (094) Kanebuchi Chemical Industry Co., Ltd. Representative Taka 1) Agent 4) Address 540 Kyobashi, Higashi-ku, Osaka 3-60 North Building 5
Subject of amendment (1) Contents of amendment in column 6 of "Detailed Description of the Invention" of the specification (1) The following sentence should be inserted between lines 10 and 11 on page 29 of the specification.

[Reference Example 6 70 parts of 2-ethylhexyl acrylate, 30 parts of vinyl acetate
1 part, 2 parts of acrylic acid, 150 parts of ethyl acetate, and 0.3 parts of benzoyl peroxide were placed in a reaction vessel, and the reaction was carried out at 80° C. for 6 hours with stirring under a nitrogen atmosphere. The obtained copolymerization solution had a solid content concentration of 39.8% and a viscosity of about 60 poise (20° C.). (2) Insert the following sentence between lines 4 and 5 on page 32 of the specification.

[Example 10 Hydrolyzable silicon group-containing polyoxyalkylene obtained in Reference Example 1 was added to 250 g of the copolymer solution obtained in Reference Example 6.
was added and mixed to obtain a homogeneous solution. The curing catalyst prepared in Reference Example 5 was added to this solution in an amount such that 3 g of DOP of the catalyst was added. Pot life, storage stability, curability, and adhesive strength were measured in the same manner as in Examples 1 to 6. The results are shown in Table 1.

Reference Example 11 To 250 g of the copolymer solution obtained in Reference Example 6, 2500 g of a toluene solution (solid content: 40 parts) of a terpene-phenol resin (YS Polystator-100, manufactured by Yasushi Oil Co., Ltd.) was added.
Added and mixed. 500 g of this mixed solution was mixed with 100 g of the hydrolyzable silicon group-containing polyoxyalkylene obtained in Reference Example 1.
In addition, after obtaining a uniform solution, the curing catalyst prepared in Reference Example 5 was added in an amount such that 3 g of DOP of the catalyst was added, and the pot life and storage stability were evaluated in the same manner as in Examples 1 to 6. , curability and adhesion were measured. The results are shown in Table 1. (3) Table 1 on page 33 of the specification is amended as follows.

Claims (1)

[Claims] 1(A) At least one hydrolyzable 3E1 in one molecule
polyoxyalkylene having a group and (B) P −
A thermosetting resin composition containing as an active ingredient a curing catalyst containing an organic acidic phosphoric acid compound having an OH bond and an amine compound. 2 The organic acidic phosphoric acid compound has the general formula %) [wherein R1 and R2 are organic residues, n is 0 or 1,
'X and y are 0.1 or 2, and x+y is 1 or 2.' 6. The composition according to claim 1, wherein the amine compound is a secondary or 6th class amine. 4. The composition according to claim 1, wherein the amine compound is an amine compound having a hydrolyzable silicon group. 5. The composition according to claim 1, wherein the main chain of the polyoxyalkylene is substantially a polymer of oxyalkylene having 1 to 4 carbon atoms. 6. The molecular weight of the polyoxyalkylene is::, 5. o
oo~, 15,000. The composition according to claim 1. 7. The composition according to claim 1, wherein the polyoxyalkylene has a hydrolyzable silicon group at the end of its molecule. 8. The composition according to claim 1, wherein the curing catalyst is blended in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyoxyalkylene. 9. The composition according to claim 1, wherein 20 to 120 parts by weight of a compatible tackifying resin are added to 100 parts by weight of the polyoxyalkylene.