JPH0848949A - Production of thermosetting self-adhesive tape - Google Patents

Abstract

PURPOSE:To provide a process for producing a thermosetting self-adhesive tape which has pressure-sensitive adhesive properties at normal temp. and thermally cures to develop adhesive strength without requiring temp. elevation or a large amt. of a solvent at the step of mixing or coating by compounding a specific polymer with a thermosetting phenol resin. CONSTITUTION:This thermosetting self-adhesive tape is produced by thermally mixing 100 pts.wt. satd. hydrocarbon polymer having at least one reactive silicon group of the formula [wherein R<1> and R<2> are each a 1-20C alkyl, 6-20C aryl, 7-20C aralkyl, or a triorganosiloxy group of (R')3SiO-(wherein R' is a 1-20C monovalent hydrocarbon group); X is hydroxyl or hydrolyzable; (a) is 0-3; (b) is 0-2; and (m) is 0-19 provided a+mb>=1] having hydroxyl or hydrolyzable groups bonded to silicon atoms and capable of forming a siloxane bond to cross-link, 20-120 pts.wt. thermosetting phenol resin, and if necessary a silanol condensation catalyst, an antioxidant, etc., kneading the mixture or dissolving it in a small amt. of a solvent to adjust the viscosity, coating a film or sheet, etc., with the mixture or soln., and drying the resultant coating layer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a novel thermosetting adhesive tape.

[0002]

2. Description of the Related Art A thermosetting adhesive tape is an adhesive tape which exhibits pressure-sensitive adhesiveness at room temperature and is further cured by heating to exhibit a strong adhesive force. Such an adhesive tape is used when a stronger adhesive force than that of a normal adhesive tape is required. As the thermosetting pressure-sensitive adhesive tape, one in which natural rubber is used as a rubber component and a phenol resin is added has been conventionally proposed.

However, since the compatibility between the phenol resin and the natural rubber is poor, there is a drawback that a large amount of the phenol resin cannot be blended. For this reason, although a method has been proposed in which a phenol resin is formed in the form of a magnesia complex compound to have compatibility with it, this method also has a limitation on the amount of the phenol resin used, and the adhesive strength after curing is not sufficient. There was a flaw.

When a thermosetting pressure-sensitive adhesive tape using natural rubber as a rubber component is manufactured, phenol resin or the like is added to natural rubber and then the tape or the like is coated, but the natural rubber is usually solid. Therefore, it is necessary to raise the temperature at the time of adding the resin or at the time of coating, or to use a large amount of solvent, which causes a problem that the operation is complicated.

[0005]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a thermosetting pressure-sensitive adhesive tape which has pressure-sensitive adhesiveness at room temperature and is further cured by heating to exhibit good adhesiveness. Is to provide a method for manufacturing the same.

Another object of the present invention is to produce a thermosetting adhesive tape which does not require the temperature to be raised or a large amount of solvent to be used when a phenol resin or the like is added or coated on a substrate. Is to provide a method.

[0007]

The above object of the present invention is to provide a mixture containing a saturated hydrocarbon organic polymer having at least one reactive silicon group in the molecule and a thermosetting phenol resin as active ingredients. Was applied to a base material and the saturated hydrocarbon organic polymer was cured at a temperature not higher than the curing temperature of the phenol resin, which was achieved by a method for producing a thermosetting pressure-sensitive adhesive tape. .

Further, the pressure-sensitive adhesive tape obtained by the production method of the present invention exhibits pressure-sensitive adhesiveness at room temperature and further hardens by heating to exhibit a strong adhesive force, so that it is used as a so-called adhesive tape. .

The present invention will be described in detail below. In the present invention, a saturated hydrocarbon polymer having a silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of being crosslinked by forming a siloxane bond, that is, at least one reactive silicon group ( Hereinafter, a saturated hydrocarbon polymer (A) will be used. The reactive silicon group used in the present invention is a well-known functional group, and a typical example thereof is represented by the general formula (1):

[0010]

Embedded image (In the formula, R ¹ and R ² are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 7 carbon atoms.
20 aralkyl group, or (R') ₃ SiO- (R'
Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different. ) Represents a triorganosiloxy group, and when two or more R ¹ and R ² are present, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more are present, they may be the same or different. a is 0, 1, 2 or 3 and b is 0, 1 or 2,
a + mb ≧ 1. Also, m

[0011]

Embedded image B need not be the same. m is 0 or 1-1
It is an integer of 9. And a group represented by).

The hydrolyzable group in the general formula (1) is not particularly limited and may be a conventionally known hydrolyzable group. Specific examples thereof include a hydrogen atom, an alkoxy group and an acyloxy group. , A ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, an alkenyloxy group and the like. Of these, an alkoxy group is particularly preferable because it has mild hydrolyzability and is easy to handle.

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

The number of silicon atoms forming this reactive silicon group is 1
The number may be one or two or more, but in the case of silicon atoms connected by a siloxane bond or the like, it is preferable that the number is 20 or less. In particular, the formula:

[0015]

[Chemical 3] (In the formula, R ² , X and a are the same as above.) The reactive silicon group represented by the formula is preferred because it is easily available.

The reactive silicon group is present in at least one, preferably 1.1 to 5, in one molecule of the saturated hydrocarbon polymer. When the number of reactive silicon groups contained in the molecule is less than 1, the curability becomes insufficient and it becomes difficult to exhibit good rubber elasticity behavior.

The reactive silicon group may be present at the terminal of the saturated hydrocarbon polymer molecular chain, may be present inside, or may be present at both ends. In particular, when the reactive silicon group is present at the terminal of the molecular chain, the effective hydrocarbon chain content of the saturated hydrocarbon polymer component contained in the finally formed cured product is large, so that high strength and high elongation are obtained. It is preferable in that a rubbery cured product can be easily obtained. Further, these saturated hydrocarbon polymers having a reactive silicon group may be used alone or in combination of two or more kinds.

The saturated hydrocarbon polymer used in the present invention is a concept which means a polymer which does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and the reactive silicon group used in the present invention. The polymer serving as the skeleton of the saturated hydrocarbon polymer having is can be obtained by the following method.

(1) A method of polymerizing an olefin compound having 1 to 6 carbon atoms such as ethylene, propylene, 1-butene and isobutylene as a main monomer. (2) A method in which a diene compound such as butadiene or isoprene is homopolymerized or the above olefin compound and a diene compound are copolymerized and then hydrogenated.

Among these polymers, an isobutylene-based polymer and a hydrogenated polybutadiene-based polymer are preferable in that a functional group can be easily introduced into the terminal, the molecular weight can be easily controlled, and the number of terminal functional groups can be increased. It is preferably a polymer.

In this isobutylene-based polymer, all of the monomer units may be formed of isobutylene units, and the monomer units having copolymerizability with isobutylene are preferably contained in the isobutylene-based polymer in an amount of 50% ( % By weight, and so on)
Or less, more preferably 30% or less, particularly preferably 10% or less.
It may be contained in the range of not more than%.

As such a monomer component, for example,
Examples thereof include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinylsilanes, allylsilanes and the like. Specific examples of such a copolymer component include:
For example, 1-butene, 2-butene, 2-methyl-1-butene, 3-
Methyl-1-butene, pentene, 4-methyl-1-pentene,
Hexene, vinyl cyclohexane, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyl. Dimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyltrichlorosilane Allylmethyldichlorosilane, Allyldimethylchlorosilane, Allyldimethylmethoxysilane, Allyltrimethylsilane, Diallyldichlorosilane, Dia Examples thereof include ryldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and the like.

When vinyl silanes or allyl silanes are used as monomers copolymerizable with these isobutylenes, the silicon content of the polymer is increased and the number of groups which can act as a silane coupling agent is increased, resulting in a composition obtained. The adhesiveness of the object is improved.

Further, in the hydrogenated polybutadiene-based polymer and other saturated hydrocarbon-based polymers as well as in the case of the isobutylene-based polymer, other monomer units other than the main monomer unit are used. May be included.

Further, the saturated hydrocarbon polymer used in the present invention contains butadiene within a range in which the object of the present invention is achieved.
A small amount, preferably 10% or less, more preferably 5% or less, particularly 1% or less of a monomer unit having a double bond remaining after polymerization such as a polyene compound such as isoprene may be contained.

The number average molecular weight of the saturated hydrocarbon polymer (A), particularly isobutylene polymer or hydrogenated polybutadiene polymer, is preferably about 500 to 100,000, and particularly preferably 1,000 to 30. Those having a liquid or fluidity of about 1,000 are preferable from the viewpoint of easy handling. Further, regarding the molecular weight distribution (M _w / M _n ), the narrower the M _w / M _n is, the more preferable the viscosity is at the same molecular weight.

A method for producing a saturated hydrocarbon polymer having a reactive silicon group will be described by taking an isobutylene polymer and a hydrogenated polybutadiene polymer as an example. Among the isobutylene-based polymers having a reactive silicon group described above, an isobutylene-based polymer having a reactive silicon group at a molecular end is a polymerization method called an inifer method (specifically serving as an initiator and a chain transfer agent called an inifer method). It can be produced by using a terminal functional type, preferably all terminal functional type isobutylene-based polymer obtained by a cationic polymerization method using the compound of 1. Such a manufacturing method is disclosed in JP-A-63 / 1988.
-6003, 63-6041, 63-2541
No. 49, No. 64-38407, No. 64-22904.

The isobutylene-based polymer having a reactive silicon group in the molecule is obtained by adding vinylsilanes or allylsilanes having a reactive silicon group to a monomer mainly containing isobutylene and copolymerizing the same. Manufactured by.

Further, in the polymerization for producing an isobutylene-based polymer having a reactive silicon group at the molecular end, vinylsilanes and allylsilanes having a reactive silicon group are co-produced in addition to the main component isobutylene monomer. By introducing a reactive silicon group at the terminal after the polymerization, an isobutylene polymer having a reactive silicon group at the terminal and inside the molecular chain can be produced.

Specific examples of the vinylsilanes and allylsilanes having a reactive silicon group include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, divinyldichlorosilane, divinyldimethoxysilane, and the like. Examples thereof include allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, diallyldichlorosilane, diallyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylmethyldimethoxysilane.

Regarding the method for producing the hydrogenated polybutadiene-based polymer, for example, first, the hydroxyl group of the terminal hydroxy hydrogenated polybutadiene-based polymer is converted to an oxymetal group such as -ONa or -OK, and then the general formula (2): ^{_{CH 2 = CH-R 3 -Y}} (2) ( in the formula, Y is chlorine atom, a halogen atom such as iodine atom, R ^{3 is, -R 4 -, - R 4} -OC (= O) -, -R
^4- C (= O)-(R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms, and preferable specific examples thereof include an alkylene group, a cycloalkylene group, an arylene group, and an aralkylene group). A divalent organic group selected from —CH ₂ — and R ″ —Ph—CH ₂ — (R ″ is a hydrocarbon group having 1 to 10 carbon atoms and Ph is a p-phenylene group) 2
Particularly preferred are valent groups. By reacting the organic halogen compound represented by the formula (1), a hydrogenated polybutadiene polymer having a terminal olefin group (hereinafter, also referred to as a terminal olefin hydrogenated polybutadiene polymer) can be produced.

As a method of converting the terminal hydroxyl group of the hydroxy-terminated polybutadiene-based polymer into an oxymetal group,
Alkali metals such as Na and K; metal hydrides such as NaH; metal alkoxides such as NaOCH ₃ ; Na
Examples thereof include a method of reacting with caustic alkali such as OH and KOH.

In the above-mentioned method, a terminal olefin hydrogenated polybutadiene polymer having almost the same molecular weight as the terminal hydroxy hydrogenated polybutadiene polymer used as the starting material can be obtained, but in order to obtain a higher molecular weight polymer. Before reacting the organohalogen compound of the general formula (2), methylene chloride, bis (chloromethyl) benzene,
When the molecular weight is increased by reacting with a polyvalent organic halogen compound containing two or more halogen atoms in one molecule such as bis (chloromethyl) ether, and then reacted with the organic halogen compound represented by the general formula (2). It is possible to obtain a hydrogenated polybutadiene-based polymer having a higher molecular weight and having an olefin group at the terminal.

Specific examples of the organic halogen compound represented by the above general formula (2) include allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene and allyl (chloro). Methyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl)
Ether, 1-hexenyl (chloromethoxy) benzene,
Examples thereof include allyloxy (chloromethyl) benzene, but are not limited thereto. Of these,
Allyl chloride is preferred because it is inexpensive and easily reacted.

The introduction of the reactive silicon group into the terminal olefin hydrogenated polybutadiene polymer is represented by, for example, the general formula (1) as in the case of the isobutylene polymer having a reactive silicon group at the terminal of the molecular chain. A hydrosilane compound having a hydrogen atom bonded to a group represented by the formula:

[0036]

[Chemical 4] (In the formula, R ² , X and a are the same as above.) The compound can be produced by addition reaction using a platinum-based catalyst.

Specific examples of the hydrosilane compound having a hydrogen atom bonded to the group represented by the general formula (1) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and phenyldichlorosilane; Alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, and phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; bis (dimethylketoxymate) methylsilane Examples thereof include, but are not limited to, ketoxymate silanes such as bis (cyclohexyl ketoximate) methylsilane. Of these, halogenated silanes and alkoxysilanes are particularly preferable.

The thermosetting phenolic resin used as the component (B) in the present invention is not particularly limited as long as it is a thermosetting phenolic resin.
Commonly used phenolic resins can be used. Specific examples of the phenol resin include, for example, phenol compounds such as phenol, cresol, xylenol, resorcinol, alkylphenol, and modified phenol (for example, cashew oil modified phenol, tall oil modified phenol) and aldehydes such as formalin and paraformaldehyde. Resole-type or novolac-type phenol resin obtained by condensation reaction with a system-based compound, or nitrogen obtained by condensation using ammonia or an amine-based compound as a catalyst in the reaction of the phenol-based compound and an aldehyde-based compound Examples thereof include an atom-containing phenol resin, and these may be used alone or in combination of two or more kinds.

When a novolac type phenol resin is used, a curing agent generally known as a curing agent for phenol resin such as aldehyde or hexamethylenetetramine is used together with the curing agent.

The saturated hydrocarbon-based organic polymer is cured by moisture by itself, but the thermosetting phenol resin finally undergoes a curing reaction and coexists with the saturated hydrocarbon-based organic polymer.

The thermosetting pressure-sensitive adhesive tape obtained by the production method of the present invention exhibits tackiness at room temperature because the phenol resin functions as a tackifying resin when the phenol resin is present in an uncured state. Is because
On the other hand, the adhesive strength is obtained by advancing the curing of the phenol resin itself by raising it to the curing temperature of the phenol resin.

Regarding the mixing ratio of the thermosetting phenolic resin to the saturated hydrocarbon organic resin, the thermosetting phenolic resin exhibits a very large compatibility, and thus the mixing can be carried out at any ratio. However, if the ratio of the thermosetting phenolic resin is too large, the tack of the adhesive tape at normal temperature decreases and the pressure-sensitive adhesive property at normal temperature is lost, so the mixing ratio is set in consideration of the adhesiveness at normal temperature. To be done. Therefore, it is usually preferable to use 20 to 120 parts by weight of the thermosetting phenol resin with respect to 100 parts by weight of the saturated hydrocarbon organic polymer. If it is less than 20 parts by weight, the adhesive property after thermosetting becomes insufficient, which is not preferable.

In the present invention, various components can be added in addition to the saturated hydrocarbon type organic polymer and the thermosetting phenol resin which are effective components. For example, commonly used silane coupling agents such as silanol condensation catalysts, antioxidants, UV absorbers, lubricants, aminosilanes, mercaptosilanes, and epoxysilanes that are commonly used to cure the saturated hydrocarbon organic polymers. It is preferable to add agents, pigments, foaming agents, fillers, plasticizers and the like as needed. Specific examples of silanol condensation catalysts that promote curing include, for example, tetrabutyl titanate,
Titanium esters such as tetrapropyl titanate; tin carboxylic acid salts such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate; reaction products of dibutyltin oxide and phthalate ester; dibutyltin acetylacetonate; aluminum Trisacetylacetonate; organoaluminum compounds such as aluminum trisethylacetoacetate and diisopropoxyaluminum ethylacetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octylate; butylamine,
Monoethanolamine, triethylenetriamine, guanidine, 2-ethyl-4-methylimidazole, 1,3
-Diazabicyclo (5,4,6) undecene-7 (DB
U) and other amine compounds or salts thereof such as carboxylic acids; and other known silanol catalysts such as acidic catalysts and basic catalysts. In addition, various tackifying resins may be used in combination for controlling the adhesive property or the adhesive property.

The method for preparing a mixture containing the saturated hydrocarbon organic polymer and the thermosetting phenol resin as active ingredients is not particularly limited. For example, the thermosetting phenol resin may be an organic material such as methyl ethyl ketone or toluene. It is dissolved in a solvent, and the saturated hydrocarbon organic polymer is mixed and dissolved in the solution, or the saturated hydrocarbon organic polymer and the thermosetting phenol resin are blended, and heated by using a roll or a kneader. It is possible to use a method such as kneading below, or dissolving both components by using a small amount of an appropriate solvent, adjusting the viscosity, and mixing.

The method of applying the mixture prepared as described above is not limited by the film or sheet substrate to be applied, but may be polyester film, cellophane film, acetate film, paper, glass cloth, silicone. Apply evenly on one or both sides of a film or sheet substrate such as release paper using a coater,
The desired thermosetting pressure-sensitive adhesive tape can be obtained by drying at 100 to 120 ° C for 1 to 5 minutes to cure the polyether organic polymer. When silicone release paper is used as the base material of the adhesive tape, it may be wound as it is and used as a transfer tape, or may be used as an adhesive tape after being transferred to a film or paper. Also, using a film, paper, non-woven fabric, foam sheet, etc. as the core material,
It can also be used as a double-sided pressure-sensitive adhesive tape if it is coated on both sides directly or by transfer.

The drying temperature at the time of producing the pressure-sensitive adhesive tape is a temperature at which the heat-curable phenol resin does not cure because the pressure-sensitive adhesive property at room temperature decreases as the curing of the thermosetting phenol resin proceeds during the production of the pressure-sensitive adhesive tape. And the temperature is usually preferably 120 ° C. or lower.

The thermosetting pressure-sensitive adhesive tape obtained by the production method of the present invention is heated at room temperature in the network chain of a cured product of a saturated hydrocarbon organic polymer containing at least one reactive silicon group in the molecule. The curable phenolic resin is in a thermoplastic state, that is, it remains uncured and compatibilizes with each other, and acts as a so-called tackifying resin, so it exhibits excellent pressure-sensitive adhesiveness at room temperature and is easy to apply to an adherend. Since the thermosetting phenolic resin is hardened by heating, the adhesive property is lost but a strong adhesive force is exhibited. Further, the thermosetting pressure-sensitive adhesive tape obtained by the production method of the present invention is different from the one using a conventional diene elastomer, and the main chain of the saturated hydrocarbon organic polymer is a saturated saturated hydrocarbon type. Since it is an organic polymer and the cross-linking is also a siloxane structure, it is thermally stable. Therefore, there is an advantage that it can be used in a high-temperature environment in which the saturated hydrocarbon-based organic polymer which has already been cured does not decompose when the phenol resin is cured.

[0048]

The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Production Example 1 Production of Saturated Hydrocarbon Polymer (A) In a four-necked flask equipped with a stirrer and a nitrogen line, 560 mL of dried methylene chloride and 116-n-hexane were mixed.
0 mL, 940 mg of α-methyl pyridine and 22 g of p-dicumyl chloride were weighed to form a uniform mixed solution, and the temperature was -70 ° C.
After cooling to room temperature, 570 mL of isobutylene monomer was charged under reduced pressure through a Molecule Sieves tube.

In the above reaction solution cooled to -70 ° C,
A polymerization catalyst solution (titanium tetrachloride 14
(mL / methylene chloride 80 mL) was added all at once to initiate polymerization. Once the temperature is raised to -54 ° C, it will be -7 in about 17 minutes.
The temperature was lowered to 0 ° C. About 20 minutes after the start of polymerization, 1,9-
Add 132 g of decadiene and further at -70 ° C for 4 hours,
Stirring was continued.

The turbid reaction solution was mixed with 3 L of warm water (about 45
(° C), the mixture was stirred for about 2 hours, the organic layer was separated, and washing with pure water was repeated 3 times. The colorless and transparent organic layer thus obtained was concentrated under reduced pressure to obtain about 400 g of an isobutylene oligomer having vinyl groups at both ends.

Next, 400 g of the vinyl group-containing isobutylene oligomer thus obtained was added to 200 mL of n-heptane.
Dissolved in water, heated to about 70 ° C, and then added with methyldimethoxysilane 1.5 [eq / vinyl group] and platinum (vinyl siloxane) complex 1 × 10 ^-4 [eq / vinyl group] to carry out hydrosilylation reaction. I went. The reaction was traced by FT-IR, and the olefin absorption at 1640 cm ^-1 disappeared in about 4 hours.

By concentrating the reaction solution under reduced pressure, an intended isobutylene oligomer having a reactive silicon group at both ends and having a molecular weight of 5300 was obtained. [Structural formula]

[0053]

Embedded image Examples 1 to 4 Sumilite Resin PR-12687 (a hexamethylenetetramine-containing cashew-modified novolac-type phenol resin manufactured by Sumitomo Bakelite Co., Ltd.) in 25% methyl ethyl ketone and Sumilite Resin PR-50775 (manufactured by Sumitomo Bakelite Co., Ltd.) Hexamethylenetetramine-containing alkylphenol-modified novolac-type phenol resin) 25% solution (toluene: methyl ethyl ketone =
A 2: 1 mixed solution was prepared, and this was mixed with 100 parts by weight of the polymer having a reactive silicon group obtained in Production Example 1 at a ratio (solid content ratio) shown in Table-1. 2'-
A solution was prepared by adding 1 part by weight of methylenebis (4-methyl-6-t-butylphenol) and 10 parts by weight of a 50% toluene solution of aluminum trisethylacetate and thoroughly mixing them. This solution is applied to a polyester film having a thickness of 50 μm and dried at 120 ° C. for 5 minutes,
An adhesive tape having a paste thickness of about 80 μm was obtained.

As the physical properties of the obtained pressure-sensitive adhesive tape, tack and 180 ° peeling adhesive strength were measured according to the methods shown below. The results are shown in Table 1 below. It was measured at a tilt angle of 30 ° and an ambient temperature of 23 ° C. according to the tilting ball tack method of the Tuck J. Dow type. The numerical value represents the size of the steel ball, and the larger the numerical value, the more preferable. 180 ° peeling adhesive strength The obtained adhesive tape was attached to a stainless steel plate, and the room temperature (about 2
180 ° peel adhesion strength (300n) after leaving at 165 ° C for 3 minutes, then leaving at 165 ° C for 20 minutes, or after leaving at 165 ° C for 60 minutes.
m / min). Comparative Example 1 As a comparative example, 75 parts by weight of a non-thermosetting phenol resin was added to 100 parts by weight of the polymer of Production Example 1, and 2,2′-methylenebis (4-methyl-6-t) was added in the same manner as in Example 1.
-Butylphenol) and 10 parts by weight of a 50% toluene solution of aluminum trisethyl acetate were added to obtain an adhesive solution. An adhesive tape was produced from this solution in the same manner as in Example 1 and its performance was evaluated. The results are also shown in Table 1 below. Comparative Example 2 As a comparative example, a solution having exactly the same composition as that of Example 3 was used, and a polyester film having a thickness of 50 μm was applied so that the glue thickness after drying was 80 μm, and then suddenly dried at 165 ° C. for 20 minutes. The performance of the obtained adhesive tape was evaluated in the same manner as in Example 1. The ball tack of this tape was 1 or less, and it was impossible to evaluate the 180 ° peel adhesive strength without contact tack. The results are also shown in Table 1 below. Comparative Example 3 As Comparative Example, the same as Example 1 except that the polymer of Example 1 was changed to a polyether organic polymer (molecular weight 8000). The results are shown in Table-1.

[0055]

[Table 1]

As is clear from the results in Table 1 above, the thermosetting pressure-sensitive adhesive tape obtained by the production method of the present invention has tackiness at room temperature and exhibits a strong adhesive force when heat-treated. It can be seen that it has excellent performance. Furthermore, it can be seen that the mechanical properties and the adhesive strength are significantly improved as compared with the polyether organic polymer. Examples 5 to 7 25% solution of SUMILITE RESIN PR-50775 (hexamethylenetetramine-containing alkylphenol-modified novolac type phenol resin manufactured by Sumitomo Bakelite Co., Ltd.) (mixed solution of methylethylketone: toluene = 2: 1)
Polymer 1 having a reactive silicon group obtained in Production Example 1
After mixing 00 parts by weight in solids at the ratio shown in Table-2,
A solution was prepared by adding 1 part by weight of 2,2′-methylenebis (4-methyl-6-t-butylphenol) and 10 parts by weight of a 50% toluene solution of aluminum trisethylacetoacetate and thoroughly mixing them. This solution was coated on a silicone release paper and dried at 120 ° C. for 5 minutes to obtain a transfer tape having a paste thickness of about 80 μm. A part of this transfer tape was transferred onto a poly film having a thickness of 25 μm, and tack, adhesion and holding power were measured. The rest was transferred to an Al plate and the tensile shear adhesive strength and T-type peel adhesive strength were measured.

The tackiness of the obtained adhesive tape was measured in the same manner as in Examples 1 to 4 above.
Further, the adhesive force, the holding force, the tensile shear adhesive strength and the T-type peel adhesive strength were measured according to the methods described below. The results are shown in Table 2 below. Adhesiveness A stainless steel plate is used as an adherend according to JIS Z-0237, and the peeling speed is 300 mm / min and the ambient temperature is 23 ° C.
Was peeled by 180 °. The holding pressure-sensitive adhesive tape was cut into a size of 25 mm × 25 mm, adhered to a stainless steel plate adherend, a load of 1 kg was applied at an ambient temperature of 100 ° C., and a moving distance after 60 minutes had elapsed was measured. It is preferable that the moving distance is short. The surface of a tensile shear adhesive strength aluminum plate (100 mm × 25 mm × 2 mm A-1050P aluminum plate specified in JIS H4000) was lightly wiped with acetone, and then the transfer tape was placed on the surface of about 25 mm × 12.5 mm. Was pasted (transferred) to an area of the same size, and another same aluminum plate was pasted onto it and crimped by hand. This sample
After curing the phenol resin by heating at 165 ° C. for 20 minutes or 60 minutes according to JIS K6850, the maximum load until the adhesive part of the test piece is broken is measured at a pulling speed of 5 mm / 5 min, The tensile shear strength was obtained by dividing the obtained value by the shear area. T-type peel adhesive strength aluminum plate (200 mm x 25 mm x 0.1 mm A-1050P specified in JIS H4000)
After gently wiping the surface of the aluminum plate) with acetone,
Approximately 100mm x the above transfer tape with a spatula
It was stuck (transferred) on an area having a width of 25 mm, and another same aluminum plate was stuck thereon, and pressure-bonded repeatedly with a 5 kg hand roller 5 times so as not to reciprocate in the length direction. This sample is run at 165 ° C for 20 minutes or 6
After heating for 0 minutes to cure the phenol resin, it was attached to a T-type in a tensile tester, and the strength when the glue part was broken was determined as T-type peel strength at a tensile speed of 200 mm / min. Example 8 γ- (2-aminoethyl) aminopropyltrimethoxysilane was added to the mixture obtained in Example 7 in an amount of 1. to 100 parts by weight of the polymer having a reactive silicon group of Production Example 1.
An adhesive tape was produced in the same manner as in Example 7 except that 0 part by weight was added, and the tack, the adhesive force, the holding force, the tensile shear adhesive strength, and the T-type peel adhesive strength were examined. The results are shown in Table 2 below. Comparative Example 4 Instead of 20 parts by weight of PR-50775 as a comparative example,
An adhesive tape was prepared in the same manner as in Example 5, except that 100 parts by weight of the polymer of Production Example 1 was mixed with 75 parts by weight of a thermoplastic aromatic petroleum resin (FTR6100, manufactured by Mitsui Petrochemical Industry Co., Ltd.). It was produced and its performance was evaluated. The results are also shown in Table 2 below.

[0058]

[Table 2]

As is clear from the results in Table 2 above, the thermosetting adhesive tape obtained by the production method of the present invention has adhesiveness at room temperature, and exhibits even stronger adhesive strength when heat-treated. You can see that it exerts an excellent effect.

[0060]

According to the production method of the present invention, a thermosetting pressure-sensitive adhesive having pressure-sensitive adhesiveness at room temperature, further curing by heating to exhibit a strong adhesive force, and thermally stable properties. It is possible to obtain a tape, and there is an effect that it can be suitably used for various applications including, for example, electrical insulation, damping steel plate use, and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C09J 115/00 JEC 123/02 JCB 161/06 JES

Claims (1)

[Claims] 1. A saturated hydrocarbon polymer having (A) a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon-containing group which can be crosslinked by forming a siloxane bond, and ( B) A thermosetting phenolic resin is contained, The manufacturing method of the thermosetting adhesive tape characterized by the above-mentioned.