JPH0395286A - Adhesive for cyclic olefin resin - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention +4 relates to an adhesive for bonding a shaped body made of a cyclic olefin resin.

Enso△Igomeki Cyclic olefin polymer (converted) It has excellent properties such as transparency, heat resistance, chemical resistance, electrical properties, mechanical strength, and formability.In addition, this shaped body has excellent dimensions. It also has stability.

Such cyclic olefin polymers can be mixed together,
Furthermore, if the cyclic olefin polymer can be bonded to other materials, especially other resins or metals, the field of application of the cyclic olefin polymer will expand.

Mendantachitan 1 The present invention (9) An object of the present invention is to provide an adhesive for a cyclic olefin resin.

1. The cyclic olefin resin adhesive according to the present invention contains at least one solvent selected from the group consisting of an aromatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, and a halogenated hydrocarbon solvent.
type of solvent, a ring-opening polymer or ring-opening copolymer formed by ring-opening polymerization of a cyclic olefin represented by the following formula [I], a hydrogenated product thereof, and ethylene and the following. At least one type of cyclic olefin polymer selected from the group consisting of a copolymer with a cyclic olefin represented by the formula [■], and a modified product of these polymers.
It is characterized in that it is contained in an amount of 0.001 to 100 g.

[I] Only one In the above formula [], n is 0 or 1, m is 0 or a positive integer, and R1 to RI@ are each independent! λ An atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. -R1●1 inversion They may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond, and RIS and Rl
6 or Rl7 and Ril1 may form an alkylidene group.

By using the adhesive according to the present invention, it is possible to easily bond using a cyclic olefin resin, which has conventionally been considered not to have good adhesive properties. Furthermore, since no resin other than the cyclic olefin resin is used as the adhesive, there is no change in properties due to changes in the resin composition. The bonding method of the present invention is particularly useful when bonding cyclic olefin resins together.

The cyclic olefin resin adhesive according to the present invention will be explained in detail.

The cyclic olefin resin adhesive according to the present invention is made by dissolving a specific amount of a cyclic olefin polymer in a specific solvent.

In the present invention, the solvent used is any one of an aromatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, and a halogenated hydrocarbon solvent.

Examples of aromatic hydrocarbon solvents used in the present invention include: benzene, toluene, xylene, phenol, ethynolebenzene, styrene, divinylbenzene,
Mention may be made of cumene and cymene.

In addition, examples of alicyclic hydrocarbon solvents include mono-converted cyclobentane, cyclobentene, cyclobentadiene, cyclohexane, cyclooctane, dicyclobentadiene, ethylnorbornene, dodecahydronaphthalene, and those represented by the above formula [I]. Among the compounds, mention may be made of compounds that are liquid at the temperature of use.

Furthermore, examples of halogenated hydrocarbon solvents include (daitrichloromethane, dichloroethane, 1,1.1-trichloroethane, carbonated tetrachloride 1,2-dichloropropane, chlorobenzene, dichlorobenzene, chlorotoluene, chloro Mention may be made of styrene and chloroxylene.These solvents can be used alone or in combination.

Among these solvents, aromatic hydrocarbon solvents and halogenated hydrocarbon solvents have particularly good solubility in cyclic olefin resins, so it is preferable to use solvents containing these as their main constituents. Further, among these solvents, it is particularly preferable to use toluene, dichloroethane, xylene, benzene or cyclohexane. These preferred solvents 1 40% by volume in the total amount of solvent
It is preferable that it is contained in the above amount.

Adhesive of the present invention (9) Contains the above solvent and a specific cyclic olefin polymer.

Cyclic olefin polymer IL used in the present invention
O, 001 to 100 per 100 ml of solvent
Contains an amount of g. By adjusting the amount of the polymer as described above, the viscosity of the adhesive does not become excessively high, and moreover, good adhesive strength is developed. Furthermore, by including the copolymer in an amount of 0.5 to 10 g,
A very good balance between adhesive strength and viscosity.

In the present invention, the cyclic olefin-based polymerization dormancy compounded in the above-mentioned solvent (a) a ring-opening polymer or a ring-opening copolymer formed by ring-opening polymerization of a cyclic olefin represented by the above formula [I1, These hydrogen additives, (b) a copolymer of ethylene and the above-mentioned cyclic olefin represented by I1 (hereinafter sometimes referred to as r-cyclic olefin random copolymer), modification of this copolymer; At least one type of cyclic olefin polymer selected from the following.

(Left space below) The cyclic olefin (transformed) represented by the above formula [I1] and the corresponding olefins are combined into
It can be easily produced by condensation using an Alder reaction.

As a cyclic olefin represented by the formula [r, specifically, bicyclo[:2, 2. 1] Hepto 2
-Ene derivative; CHs 9-inputyl-2.7- 9, 11. 12-trimethyl9-ethyl-11. 12-dimethene 5.10-dimethyltetra 2,7. 9-}Limethylte9-isobutylene11. 12 5, 8, 9. 10-tetramethy8-methyltetrasic8-ethyltetrasic+1]-3-dodecene8-hexyltetracy5.17 l●]-3-dodecene16]-3-dodecene-13-dodecene1 @]-3-dodecene 12. s, 1t +1]-3-dodecene 1 @]-3-dodecene8-methyl-9-ethylte8-chlorotetracyc8-promotetracyc8-fluorotetracy1●co-3-dodecene1m]-3-dodecene 8-ethylidene-9-iso-dodecene. 12 s, 17 1]-3-dodecene 5, 1〒・1e-3-dodecene 8-n-propylidene-9 1-dodecene 8-n-propylidene-9 8-isopropylidene [4, 4, 0. 12 S, 17 1@]-3-dodecene-dodecene+1]-3-dodecene1 1 ]-3-dodecene8-n-propylidene-9 8-isopropylidene[4. 4, 0. 1" 5.1? +1]-3 Dodecene - Tetracyclo such as dodecene [4, 4, 0.12・S.l
1-3-dodecene derivative; (blank below) 8-isopropylidene 24-4-heptadecene + 3, Q2. 〒O9+a3-4-Heptadecene etc. [6, 6, 1. 136. ll
ll. +3, Q2. ? , Q* Decene + j co-4-heptadecene derivatives; octasic [8, 8, 0. 129,14 Ma ll+ 1I 3. I I, Q3. @ , Ql 21te]-5-docosene derivative; heptasic [8, 7. 0 Hebutacyclo-5-icosene derivatives such as cosene 1/)i
Yohebutacyclo-5-heneicosene derivatives; pentacyclos such as decene [6,6,1, p6,02. Lower Q
9+ 4 ] -4- Hexadecene derivatives 5-methyl-tricyclo 1,3-dimethyl-benta and other tricyclo[:4, 3. 0. 1”5 ko 3
-Decene derivative: 1,6-dimethylpenta10-methyl-trisic14. [4, 4, 0. 12・S]13
- pentacyclo [6, 5, 1
．． 13.6,02.7.00+31-4-pentadecene derivatives; diene compounds such as 21,113.2@, Ql4. +9,115・18 5-Pentacosensen, etc.
,111.12]-3-pentadecene derivative; cosene'3.2+1,Q14.19.11.111]-5-pentacocene, etc. / None') T:! [9,10,1.1'-
',03ll,O"",01221,1112fl,Q
14.19. ll. Mention may be made of Ill-5-pentacocene derivatives.

(Left below) 2・l]-4-eicosene etc. Nohep9 sikl:+ [7,8,0,13. ',
02・〒,11”-1?,0th・+s,l+*.+J
-4-eicosene derivative: used in the present invention (
a) 1 ring-opening polymer or ring-opening copolymer formed by ring-opening polymerization of the cyclic olefin represented by the formula [rl] The cyclic olefin represented by the formula [I3, for example, ruthenium, rhodium, palladium, osmium, It is obtained by ring-opening polymerization in the presence of a catalyst consisting of a metal halide, nitrate, or acetylacetone compound such as indium or platinum, and a reducing agent such as alcohol.

These may be homopolymers or copolymers of inverted cyclic olefins. For example, 1,4,5,8-dimethano-1. 2, 4, 4a, 5. 8, 8a-Octahydronaphthalenes polymerized together, and the above naphthalenes and norbornene (e.g. bicyclo[
2, 2. 11hept-2-ene) may be copolymerized.

The double bond IL remaining in the above ring-opened polymer or copolymer can be easily hydrogenated using a known reduction catalyst. IL such hydrogenates can also be used in the present invention. By using such a hydrogenated product, a polymer with excellent thermal stability and weather resistance can be obtained.

In addition, when performing ring-opening polymerization, a cyclic olefin other than the cyclic olefin represented by the above formula [I1 can be subjected to ring-opening polymerization within a range that does not impair the properties of the resulting polymer. Such cyclic olefins include cyclobutene, cyclopentene, cyclohexene, 3.4-
Dimethylcyclohexene, 3-methylcyclohexene,
2-(2-methylbutyl)-1-cyclohexene, 2,
3, 3a, 7a-tetrahydride-4,7-methanol IH-indene, 3a, 5, 6, 7a-te1.
Examples include lahydro-4,7-methanol IH-indene. These other cyclic olefins can be used alone or in combination and are typically O
It is used in an amount of ~20 mol%.

(b) Cyclic olefin random copolymer +L used in the present invention It is obtained by copolymerizing ethylene and a cyclic olefin compound.

In the cyclic olefin random copolymer, the molar ratio of ethylene component to cyclic olefin component is usually 10:90.
~90:10, preferably 50:50-75:25
used within the range of This cyclic olefin random copolymer is produced by polymerizing ethylene and a cyclic olefin in a hydrocarbon solvent in the presence of a catalyst formed from a hydrocarbon-capable vanadium compound and a halogen-containing organoaluminum compound. can do.

Examples of the hydrocarbon solvent used in the present invention include aliphatic hydrocarbon milk, alicyclic hydrocarbons, and aromatic hydrocarbons. Furthermore, among the monomers used in the preparation of the cyclic olefin copolymer, compounds that are liquid at the reaction temperature can also be used as the reaction solvent. These solvents can be used alone or in combination.

In the present invention, the vanadium compound used as a catalyst is the formula V○(OR), Vb or the formula V(OR). Examples include compounds represented by X.

In the above formula, R is a hydrocarbon group, O≦a≦3
, 0≦b≦3, 2≦a+b≦3, 0≦C≦4, O≦d≦
4, 3≦c+d≦4.

These vanadium compounds can be used alone or in combination.

Such a vanadium compound sample may be an electron donor adduct of the vanadium compound represented by 2 above.

In addition, examples of electron donors that form adducts with the above vanadium compounds include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, alkoxysilanes, etc. Nitrogen-containing electron donors such as ammonia, amines, nitriles, incyanates, etc. can be mentioned.

A compound having at least one AI2-carbon bond in one inversion molecule can be used as an organoaluminum compound used as a catalyst together with the above vanadium compound.

An example of an organoaluminum compound that can be used in the present invention is one having the formula Rl. All (OR”)n H, X. (
In the formula, Rl and R2111-15 images are preferably 1-
Hydrocarbon groups containing 4 carbon atoms may be the same or different from each other. X is halogen, m is 0≦m≦3, n is O≦n<3, p is 0≦n<3, q is a number such that O≦q<3, and m+n+p+q=3. ) Organoaluminum compounds (11) 2M+AQR+a (In the formula, Ml is LiS Na, K, and Rl has the same meaning as above) A complex alkylated product of a Group 1 metal and aluminum, etc. can be mentioned.

Concentration IL of the above vanadium compound in the reaction system
Vanadium compounds usually have a vanadium atom of 43
0.01 to 5 gram atoms/y, preferably 0.01 to 5 gram atoms/y. 0
It is used in an amount of 5-3 gram atoms/9.

In addition, the organoaluminum compound has a ratio of aluminum atoms to vanadium atoms (AQ/V) in the polymerization reaction system.
is used in an amount of 2 or more, preferably 2 to 50, particularly preferably 3 to 20.

Such a polymerization method itself is already known, and is described, for example, in Japanese Patent Application Laid-Open No. 168708/1983.

The above-mentioned cyclic olefin random copolymer may be polymerized with other components such as a-olefin within a range that does not impair the properties of the polymer.

Such olefins include propylene, 1-butene, 4-methyl-1-bentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and - a having 3 to 20 carbon atoms, preferably 3 to 15 carbon atoms, particularly preferably 3 to 10 carbon atoms, such as eicosene;
-Olefins are used. Such a-olefins are usually used in an amount of O to 20 mol%.

In addition, the cyclic olefin components include hecyclobutene, cyclobentene, cyclohexene, 3.
4-dimethylcyclohexene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene,
cyclooctene and 3a. 5, 6. Cycloolefins such as 7a-tetrahydro-4.7-methanol IH-indene: norbornene 5-methylnorbornene-2.5-ethylnorbornene 5-isoprobylnorbornene
2. 5-n-butylnorbornene-2. 5-i
Norbornenes such as 2-fluoronorbornene-2 and 5,6-dichloronorbornene-2, styrene, methylstyrene, etc. can also be used. Such compounds are usually used in amounts of 0 to 20 mol%.

Sara↓ki Cyclic olefin random copolymer strength set [r
] The cyclic olefin represented by may contain a ring-opened repeating unit or a repeating unit derived from a hydrogenated product thereof.

In addition, other than the cyclic olefin represented by the formula El], 1.4
-hexadiene, 4-methyl-1,4-hexadiene,
Dual dienes such as S-methyl-1,4-hexadiene, 1,7-octadiene, dicyclobentadiene, 5-ethylidene-2-norbornene and non-conjugated dienes such as 5-vinyl-2-norbornene. Compounds having two or more bonds in the molecule can also be used as they are or after being partially hydrogenated.

Furthermore, the cyclic olefin random copolymer used in the present invention was measured in decalin at 135°C. Limiting viscosity [
7] it tl*0. 0 1 ~ 2 0dl
/g1 preferably O. OS~10dl/kom More preferably 0. It is within the range of 08 to 8 dl/g, and
Softening temperature (TMA) measured with a thermal mechanical analyzer
'C, preferably in the range of 90 to 230 °C, and the glass transition temperature (Tg) L is usually 50 to 2
30°C, preferably in the range of 70 to 210°C, and the crystallinity measured by X-ray diffraction is usually 5% or less,
Preferably it is substantially 0%.

In addition, the thermal decomposition temperature of this copolymer is usually 350 to 19.
420°C, preferably within the range of 370-400°C.

Further, E, the flexural modulus of this copolymer is usually 3
00 to 15004/cma, and the density is usually 0.00 to 15004/cma. 86 ~1. 1 og/cf, preferably 0. 88 ~1. 08g/crt! , and the refractive index (ASTM D542) IL is usually 1.47 to 1.58, preferably 1.48 to 1.5.
6 and is substantially amorphous, so the haze (ASTM 1003) is usually 20.
% or less, preferably 10% or less.

As for the electrical properties of this copolymer, ASTMDI 50
The dielectric constant (1kHz) measured by is usually 1.
5 to 3.05 preferably l, 9 to 2.6, dielectric loss tangent usually in the range of 9 x 1 0-4 to 8 x lO-a, preferably 3 x 10-4 to 9 x lO-s.

Modification of the polymer (C) used in the present invention, the above (a) and (b) The above cyclic olefin random copolymer is modified using an a, β-unsaturated carboxylic acid and/or a derivative thereof. Alternatively, it can be obtained by modification using a styrene hydrocarbon, or by modification using an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group, or an unsaturated epoxy monomer.

α, β monounsaturated carboxylic acid and/or
Or as a derivative thereof Even though! 4 Acrylic acid, methacrylic acid, q-ethyl acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocis-bicyclo[2, 2, 1] heptose-5-en-2,
unsaturated carboxylic acids such as 3-dicarboxylic acid (Nadic acid TM), methyl-endocysbicyclo[2,2,1]hep}-5-ene-2,3-dicarboxylic acid (methylnadic acid TM), or Examples include derivatives of unsaturated dicarboxylic acids such as acid halides, amides, imides, acid anhydrides, and esters. Specific examples of such derivatives include malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, and dimethyl maleate. These compounds may be used alone or in combination. Among these, it is preferable to use maleic acid, nadic acid, or acid anhydrides thereof.

Examples of the styrenic hydrocarbon used here include compounds represented by the following formula.

In the above formula, RIR2k and R3iL may be the same or different, and are a hydrogen atom or a lower alkyl group. Specific compounds represented by the above formula (styrene, α-methylstyrene, o, m
or p-monochlorostyrene, O,m or p-monomethylstyrene, o,m or p-monoethylstyrene% o,m or p-monoisoprobylstyrene. These can be used alone or in combination.

Among these, styrene, m-
Preference is given to using methylstyrene or p-methylstyrene.

As the organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group used here, even if l
! , compounds represented by the following formula can be mentioned.

R' R2 SiY+ Y2 RI Consisting of Specifically, examples of groups having such an olefinically unsaturated bond include a vinyl penta-acrylic penta-butenyl group, a cyclohexenyl penta-cyclobentadienyl group, and a group represented by the following formula.

CH2 SoC (C mountain) Coo (CH2 ) 3-CH2
=C(CH3)COO(CHa)2-0-(C
Ha) s-CH2=C(CH3)COOCH2-
0-CHa CH(OH)CH20(CHa)s
-Also, X is an organic group having no olefinic double bond, and is an alkyl group such as methyl, ethyl, proyl, tetradecyl, or octadecyl, or an aryl group such as phenyl, benzyl, or tolyl group.

Furthermore, YI Y2 and Y314 are hydrolyzable groups, examples of such groups include methoxy
Ethoxy group, Phtoxy group, Alkoxy group, such as methoxyethoxy group, Formyloxy group, Acetoxy group, Acyloxy group, such as propionoxy group, and residues from which a hydrogen atom has been removed from oxime as shown below: 1ON=C(CHs)a 1 〇N C H C Ha Ca Hs-ON Tomi C (
C@H6) 2. Alkyl-substituted amine group or aryl-substituted amino group as shown below; -NHCH, -NHC,H, etc. can be mentioned. In addition, YI Y2 and Y314 may each be the same or different. In particular, compounds in which YI Y2 and Y3 are the same are preferred. Among these organosilicon compounds, compounds represented by the following formula such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris(methoxyethoxy)cyan; RI SiYI Y2
It is preferable to use Y3 as well as vinylmethyldiethoxysilane, vinylphenyldimethoxysilane, and the like.

Examples of the compound used here having at least one polymerizable unsaturated bond and at least one epoxy group in the molecule include compounds represented by the following formula.

Unsaturated glycidyl esters represented by (where R is a hydrocarbon having a polymerizable ethylenically unsaturated bond &R
l represents a hydrogen atom or a methyl group).

Unsaturated glycidyl ethers represented by (however, R and Rl have the same meanings as above, epoxyalkenes represented by (however, L and R have the same meanings as above,
R214 represents an alkyl penta or an aralkyl group).

Examples of the above-mentioned compounds include glycidyl acrylate, glycidyl methacrylate, mono- and diglycidyl esters of itaconic acid, mono-, di- and tri-diglycidyl esters of butenetricarboxylic acid, mono- and diglycidyl esters of citraconic acid, endocytobicyclo 1: 2, 2. 1] Hepto 5-
Mono- and diglycidyl esters of en-2,3-dicarboxylic acid (nadic acid τM), endocycic 1
:21:2,2.1]Hepto-5-12-2-methyl-
2.3-dicarboxylic acids (mono- and diglycidyl esters of methylnadic acid rQ, mono- and diglycidyl esters of allylsuccinic acid, mono- and diglycidyl esters of p-styrenecarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, Styrene-p-glycidyl ether, 3.4-epoxy-1-butene, 3.4-epoxy-3-methyl-1-butene, 3
, 4-epoxy-1-bentene, 3,4-epoxy-3
-methyl-1-bentene, 5,6-epoxy-1-hexene, and vinylcyclohexane monoxide. These compounds can be used alone or in combination. Among these, glycidyl acrylate and glycidyl methacrylate are preferred.

A known method can be used to modify the polymers (a) and (b) using the modifiers described above.

Such a method includes a method in which a modifier is added to the above-mentioned cyclic olefin polymer to melt the polymer to produce a graft copolymer, or a method in which the modifier is dissolved in a solvent and the solution is mixed with the polymer. Examples include a method of modifying the polymer by mixing it with a cyclic olefin polymer. In such a method, it is preferable to use a transposition radical initiator in order to efficiently carry out graft modification. The radical initiator used here is not particularly limited, and conventional initiators such as organic peroxides, organic peresters, and azo compounds can be used. Further, the reaction can be carried out by irradiating energy beams such as electron beams or ultraviolet rays without using an initiator or an initiator.

For example, in the modified cyclic olefin radham copolymer produced as described above, the intrinsic viscosity [η] measured in Tecarin at 135°C is usually +10. 03
~20 dl/c Good mat, <Ha o. 05-5
It is within the range of di/g.

Furthermore, the glass transition temperature measured using a dynamic viscosity meter (DMA) (typically 20-250°C, and 30-30°C)
The temperature is in the range of 220°C, and it is extremely resistant to hot water. In addition, the softening point of such a cyclic olefin random copolymer can be determined by thermo-mechanical (TMA)
When measured as the temperature when the quartz needle penetrates 0.1 m into the resin at a heating rate of 5°C/min using a quartz needle (diameter 0.635 ms) with a load of 49g1 using a 1 conversion of modified products usually 20-2
It exhibits a softening point of 30°C, often in the range 30-200°C.

Furthermore, the density of the modified cyclic olefin polymer as measured by the method specified in ASTM-D-1505 (normally 0.95 to 1.20 g)
/cl! ? , preferably 0. 9 6 ~1.
It is within the range of 10 g/cm3.

In the present invention, instead of the cyclic olefin random copolymer, the aforementioned ring-opening copolymers or hydrogenated products thereof may be used.

In the present invention, the above cyclic olefin polymer 14
L/% can be used alone or in combination. The above-mentioned cyclic olefin random copolymer may contain other fractional units, such as α-olefin fractional units, within a range that does not impair the properties of the copolymer.

There are no particular limitations on the method for producing the adhesive of the present invention using the cyclic olefin polymer as described above, and for example, the method may include mixing and dissolving the solvent as described above and a cyclic olefin resin or a modified product thereof. It can be manufactured by

The adhesive tL of the present invention produced as described above can also adhere to each other shaped bodies made of a cyclic olefin polymer and a composition containing this polymer.
Kinho, which is made of a precept form like this and other resins.
It can be used to bond ceramics, etc.

If the adhesive of the present invention is a single-ring polymer, an intercyclic copolymer, or a hydrogenated product thereof, or a cyclic olefin random copolymer or a modified product thereof, such a copolymer is 1 as a combined and modified product
4 The above-mentioned cyclic olefin copolymers can be used.

In addition, in the case where the shaped body is formed from a resin composition containing a cyclic olefin polymer, various resins such as those shown below can be used as resins for forming such a resin composition. Resin can be used.

Examples of resins that can be blended with the above cyclic olefin polymer to form a resin composition include polyethylene, polypropylene, and polymethylbutene.
Polyolefins such as poly4-methylbentene-L, polybutene-L and polystyrene (these polyolefins may have a crosslinked structure): polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, chlorinated rubber, etc. Halogen-containing vinyl polymers; a. Polymers derived from β-monounsaturated acids or derivatives thereof, copolymers such as acrylonitrile/butadiene/styrene copolymers, acrylonitrile, styrene/acrylic acid ester copolymers, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, Polymers such as polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyacryl phthalate and polyallyl melamine, as well as co-existence of monomers comprising the aforementioned polymers with other monomers, such as ethylene-vinyl acetate copolymers. Polymers; polymers with epoxy groups, such as polyethylene oxide and polymers derived from bisglycidyl ether; polyacetals, such as polyoxymethylene, polyoxyethylene and polyoxymethylene containing ethylene oxide as a comonomer; polyphenylene oxide; polycarbonates; polysulfones; polyurethane and urea resins; polyamides or copolyamides such as nylon 6, nylon 66, nylon 11 and nylon 12; polyesters such as polyethylene terephthalate, polybutylene terephthalate, poly 1,4-dimethylol cyclohexane terephthalate and polyethylene naphthalate; phenols - Formaldehyde resin - Polymers with crosslinked structures such as urea - formaldehyde resin and melamine - formaldehyde resin - Alkyd resins such as glycerin - phthalic acid resin - Derived from copolyesters of saturated or unsaturated dicarboxylic acids and polyhydric alcohols Unsaturated polyester resins crosslinked with vinyl compounds and resins in which at least some of the hydrogen atoms present in these resins have been replaced with halogen atoms Celluloses such as cellulose acetate, cellulose propionate and cellulose esters; rubbers and proteins; These derivatives; a-olefin copolymers, a-olefin/diene copolymers, aromatic vinyl hydrocarbon/conjugated diene soft copolymers, and inbutylene or isobutylene/conjugated as shown below. Mention may be made of soft polymers consisting of Jen.

The a-olefin copolymer used herein is a non-quality or low-crystalline copolymer consisting of at least two types of a-olefins. A specific example is a copolymer of ethylene and a q-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms. The molar ratio L40 to the component unit is preferably within the range of 60 to 9S; 5.

In addition, when the α-olefin is propylene, the ratio of the above ethylene component unit and propylene component unit is 4.
The ratio is preferably in the range of 0:60 to 90:10, and when the α-olefin is a Q-olefin having 4 or more carbon atoms, the above ratio is preferably in the range of 145,050 to 95;5. preferable.

Further, as the σ-olefin copolymer, a copolymer formed from propylene and an a-olefin having 4 to 20 carbon atoms can be used, and in this case, a certain unit of propylene and an a-olefin copolymer may be used. The molar ratio to the minute unit is 50:
It is preferably within the range of 50-95:5.

As an α-olefin/diene copolymer used as a soft polymer, 14 specifically 1-turn ethylene/a-
Olefin/diene copolymer rubber and propylene/a-olefin diene copolymer rubber are used. The dienes used herein include 1,4-hexadiene, 1.
Linear non-conjugated dienes such as 6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene and 7-methyl-1,6-octadiene: cyclohexadiene, dicyclobentadiene , methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, and 6-chloromethyl-5-improbenyl-2-norbornene, etc. Cyclic non-conjugated diene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-impropylidene-5-norbornene, 2-probenyl-
Other dienes such as 2,2-norbornene may be mentioned. In addition, when a plurality of a-olefins are used, the molar ratio of each olefin is the same as in the case of the a-olefin copolymer, and the content of diene components in this copolymer is usually is 1 to 20 mol%, preferably 2 to 15 mol%.

Aromatic vinyl hydrocarbons used as soft polymers
Specific examples of the conjugated diene-based soft copolymer include random copolymers, block copolymers, and hydrides of aromatic vinyl hydrocarbons and conjugated diene-based copolymers. Specific examples of such aromatic vinyl hydrocarbon/conjugated diene soft copolymers include styrene,
Butadiene block copolymer rubber, styrene/butadiene/styrene block copolymer rubber, styrene/isoprene block copolymer rubber, styrene/isoprene/styrene block copolymer rubber, hydrogenated styrene/butadiene/styrene block copolymer Examples include rubber and styrene-putadiene random copolymer rubber.

In these copolymer rubbers, the molar ratio of aromatic vinyl hydrocarbon to conjugated diene is usually 10:90 to 70.
: Within the range of 30. In addition, the above-mentioned copolymer rubber is a hydrogenated copolymer rubber and a copolymer rubber in which some or all of the load bonds remaining in the above-mentioned copolymer rubber are hydrogenated.

Used as a soft polymer. Specific examples of the soft polymer made of isobutylene or isobutylene/conjugated diene include 1-turn polyisobutylene rubber, polyisoprene rubber, and polyptadiene rubber/isoprene copolymer rubber.

The above-mentioned soft polymer has an intrinsic viscosity [η] measured in decalin at 11135°C, which is usually in the range of 0.01 to 10 dl/i, preferably 0.08 to 7 dl/i, and the glass transition temperature is usually is 0°C or lower, preferably -20°C or lower, and the crystallinity measured by X-ray diffraction is usually in the range of 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%. It is in.

Other resins in the composition containing the cyclic olefin resin include the cyclic olefin resin and/or its modified product 1.
It is usually used in an amount of 150 parts by weight or less, preferably 100 to 5 parts by weight.

Blending other resins with the above-mentioned cyclic olefin resins It can be produced by mixing (or mixing, %*) of cyclic olefin resins and other resins according to the usual method. By producing as described above, a polymer alloy containing a cyclic olefin resin as a main component is produced. That is, in the above polymer alloy, other resins are finely dispersed in the cyclic olefin resin, and this polymer alloy has excellent properties.

Such polymer alloys can also be used after being crosslinked. In particular, such crosslinking is useful for other resins such as rubber
It is particularly effective when containing the above-mentioned soft copolymer.

Such a crosslinked polymer alloy Imo can be produced, for example, as follows.

The above-mentioned cyclic olefin resin and the rubber, especially the above-mentioned soft copolymer, are added in an amount of 5 to 150 parts by weight paper, preferably 5 to 100 parts by weight, and more preferably 10 to 100 parts by weight, per 100 parts by weight of the cyclic olefin resin. 80 parts by weight are kneaded. The melt flow index (MFR.AS) of such polymer alloys
TM D1238 conditions) 1 turn normally 0. 1-100
It is.

To crosslink polymer alloys such as those described above, organic peroxides are typically used.

Examples of organic peroxides that can be used in the present invention include ketooxides such as 1-methylethyl ketoperoxide and cyclohexanone peroxide; 1,1-bis(t-butylbaroxy)cyclohexane, 2,2-bis(t −
baroxyketals such as (butylperoxy)octane; t-butylhydroberoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxyperoxide and 1,1,3. Hydro1<-oxides such as 3-tetramethylbutylhydroberoxide; di-t-butylperoxide, 2,5-dimethyl-2,
5-di(t-butylperoxy)hexane and 2.5
-dimethynole-2,5-di(t-butynoleveroxy)
Dialkyl peroxides such as hexine-3; lauroyl peroxide and benzoyl)<diasilver oxides such as monooxide; t-butyl peroxyacetate, t-butyl)<-oxybenzoate and 2,5-dimethyl-2,5 Examples include -oxy esters such as -di(penzoylperoxy)hexane.

The above organic peroxide is usually 0 parts per 100 parts by weight of the total weight of the cyclic olefin polymer and other resins.
．． Ol-1 is preferably used in an amount within the range of 0.05 to 0.5 parts by weight.

Further, by incorporating a compound having two or more radically polymerizable functional groups in the molecule during treatment with an organic peroxide, the properties such as impact resistance of the resulting polymer alloy are improved.

Examples of compounds having two or more functional groups in the molecule that can be used in this way include (9) divinylbenzene, (
Examples include vinyl meth)acrylate. These compounds are usually contained in an amount of 1 part by weight or less, preferably 0.0 parts by weight or less, based on 100 parts by weight of the total amount of the cyclic olefin polymer and other resins. 1~0. It is used in an amount within the range of 5 parts by weight.

Additives may be further added to the resin as described above, if desired.

Examples of additives that can be used here include: heat-resistant stabilization L, weather-resistant stabilization L, antistatic agent, slip life L, anti-blocking la, anti-fog L, smooth life L
Dyes, pigments, natural ponds, waxes, organic fillers
Mention may be made of inorganic fillers.

One example is the stability of the cyclic olefin resin as described above.

(Left below) An example of a substance that can improve the stability of the cyclic olefin resin as described above is tetrakis [methylene-3-(3.5-di-t-butyl-4-hydroxyphenyl)probionate]. Methane, β-(3,5-di-t-butyl-4-hydroxyphenyl)probionic acid alkyl ester, 2,2'-oxamidobis[ethyl-
Phenolic antioxidants such as 3-(3.3-di-t-butyl-4-hydroxyphenyl)propionate: zinc stearate, calcium stearate, 1.2-
Examples include fatty acid metal salts such as calcium hydroxystearate, polyhydric alcohol fatty acid esters such as glycerin distearate, bentaerythritol monostearate, pentaerythritol distearate, and bentaerythritol tristearate. These can be used alone or in combination. An example of such a combination is the combination of (9) tetrakis[methylene-3-(3.5-di-t-butyl-4-hydroxyphenyl)probionate]methane, zinc stearate, and glycerin monostearate. can be mentioned.

In addition, 1 is an inorganic filler that can be blended into the resin.
叡 Specifically: Silica, diatomaceous earth, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate,
Dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfate, boron fiber Mention may be made of silicon carbide fibers.

Examples of organic fillers include polyethylene fibers, polypropylene fibers, polyester fibers, polyamide fibers, polyimide fibers, and the like. These can be used alone or in combination, and can be blended in amounts within conventional ranges. Further, there is no particular restriction on the method of blending these, and for example, they can be blended into the resin by mixing with a cyclic olefin random copolymer or the like and then kneading.

By using the Jigetsu & or resin-combined Kaimono prepared as described above, for example, by employing a known method such as the injection or blowing method, extrusion or molding method, or sedimentation method. Precept forms can be manufactured for use with the adhesive of the invention. Therefore, there is no particular restriction on the shape of such a precept, and it can be shaped to correspond to a desired container shape or component material, and can also be shaped into a film or sheet.

By using the adhesive of the present invention, the resin shaped bodies obtained as described above or the above-mentioned shaped bodies are bonded to objects to be adhered such as other resins. In the present invention, IL is used as an adherend such as other resins.
For example, various materials such as ceramics made of resin other than cyclic olefin resin, dense cloth, and nonwoven fabric can be used. In particular, by employing the method of the present invention, adhesion to resin or metal becomes better.

Even if metal is used as the adherend,
As metal! Examples include rolled iron, aluminum, and stainless steel.

In addition, even if ◆f1 resin is used as the adherend, the resin may be acrylic resin, U1/tan resin,
Epoxy resin, polyolefin, polyvinyl chloride resin,
Polyester resin, polycarbonate resin, polyamide resin, polyacetal resin, polyphenylene oxide Jubuta Polystyrene Jugetsuya Acrylonitrile/styrene Jugetsu W, ABS resin, specifically polyethylene,
Polyolefins such as polypropylene, polymethylbutene-1, poly4-methylbentene-1, polybutene-1, and polystyrene (these polyolefins may have a crosslinked structure); polyvinyl chloride, polyvinylidene chloride, polyfluoride, etc. Halogen-containing vinyl polymers such as vinyl chloride, polychloroprene, and chlorinated rubber; a. Polymers derived from β-monounsaturated acids or derivatives thereof and copolymers such as acrylonitrile/butadiene/styrene copolymers, acrylonitrile, styrene/acrylic acid ester copolymers, etc.: polyvinyl alcohol, polyvinyl acetate,
Polymers such as polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyacryl phthalate, polyallyl melamine, and monomers constituting the aforementioned polymers such as ethylene-vinyl acetate copolymers, and others. Polymers with epoxy groups such as copolymers with monomers such as polyethylene oxide and polymers derived from bisglycidyl ether; Polyacetals such as polyoxymethylene, polyoxyethylene, and polyoxymethylene containing ethylene oxide as a comonomer; Polyphenylene oxide polycarbonate polysulfon; polyurethane and urea resins polyamides or cobolyamides such as nylon 6, nylon 66, nylon 11 and nylon 12; polyesters such as polyethylene terephthalate, polybutylene terephthalate, poly 1,4-dimethylol cyclohexane terephthalate and polyethylene naphthalate. Polymers with crosslinked structures such as phenol/formaldehyde resins, urea/formaldehyde resins, and melamine/formaldehyde resins; Alkyd resins such as glycerin/phthalic acid resins; Derived from copolyesters of saturated or unsaturated dicarboxylic acids and polyhydric alcohols Unsaturated polyester resins that are cross-linked with a vinyl compound and resins in which at least some of the hydrogen atoms present in these resins are substituted with halogen atoms; Celluloses such as cellulose acetate, cellulose propionate, and cellulose esters;
Rubber and protein or derivatives thereof; a-olefin copolymers, a-olefin/diene copolymers, aromatic vinyl hydrocarbon/conjugated diene soft copolymers, and isoptylene or imbutylene/conjugated Mention may be made of soft polymers consisting of dienes.

In particular, the adhesive of the present invention is suitable for adhering molded bodies formed from the above-mentioned cyclic olefin resin.

That is, by using the adhesive of the present invention, it is possible to effectively bond cyclic olefin resins that are difficult to bond with conventionally used adhesives. and,
When adhering cyclic olefin-based resin bodies such as those mentioned above, the above adhesive should not only be applied to the area to be bonded on one of the cyclic olefin resins, but also to the area where each cyclic olefin resin is to be bonded. The adhesive is applied and the adhesive force of the cyclic olefin resin dissolved in the adhesive is utilized, and at least a portion of the cyclic olefin resin on the surface of each part to be bonded is dissolved in the solvent contained in the adhesive. It is preferable to bring the copolymer into a state in which the copolymer is bonded, or in a state where the copolymer contains a solvent, so that adhesive strength is developed in each of the areas to be bonded, so that the copolymer also participates in bonding.

There is no particular restriction on the method of applying the adhesive to the above-mentioned area to be bonded. Various methods can be employed, such as a method of applying using a coating device such as a blade coater, and a method of immersing a resin or shaped body in an adhesive.

For example, the amount of adhesive applied using the method described above is usually adjusted within the range of 0.001 to 0.1 g/cm2, preferably 0.005 to 0.05 g/cm2.

The object to be adhered is brought into contact with the surface to be adhered to which the adhesive has been applied as described above, and the object is adhered.

It is preferable to adhere the bonded body formed from the above-mentioned cyclic olefin resin or the like by bringing the part to be adhered and the body to be adhered into close contact with each other under pressure.

After bringing the two into contact in this manner, the solvent contained in the adhesive is removed to bond the two.

There is no particular restriction on the method for removing the solvent, and the solvent is usually removed from the area to be bonded by leaving it at room temperature or under heating. Note that it is not necessary to completely remove the solvent 14, it is sufficient to remove it to the extent that the desired adhesive force is developed, and usually the content of the solvent on the surface to be bonded is 10% by weight or less, preferably 1% by weight or less. Practical adhesive strength is developed by removing the adhesive in such a manner.

In this manner, by using the adhesive of the present invention when bonding cyclic olefin resins, it is possible to bond shaped bodies made of cyclic olefin resins without using other resins with different characteristics. Therefore, the excellent properties of the cyclic olefin resin are maintained even on the adhesive surface.

Since the adhesive of the present invention is composed of a specific solvent and a cyclic olefin polymer, it easily adheres to molded objects made of cyclic olefin resins, which were conventionally thought not to have good adhesive properties. be able to. Moreover, since no resin other than the cyclic olefin resin is present on the adhesive surface, the excellent properties of the cyclic olefin resin are not impaired on the adhesive surface.

In particular, by employing the adhesive of the present invention when bonding cyclic olefin resins together, no other resin or the like is present between the resin shaped body made of the above copolymer and the adhered body. Since the resin composition does not change significantly, and the same copolymer is used, adhesion can be performed without substantially changing the adhesive interface. Therefore, the resin or shaped object and the object to be adhered are substantially integrated, so that extremely high adhesion strength is exhibited.

Next, the present invention will be explained with reference to Examples, but the present invention should not be construed as limited by these Examples.

(1) Melt flow index (MFRT'C) According to ASTM D1238, specified temperature T℃, load 2
．． Measured at 16 kg Circle (2) Intrinsic viscosity [7] Decalin solution Measured at 135°C 9 (3) Softening temperature (TMA) Thermo Mechanical A manufactured by DuPont
The thermal deformation behavior of a sheet with a thickness of lm was measured using a nalyzer. That is, a quartz needle was placed on the sheet, a load of 49 g was applied, and the humidity was raised at a rate of 5°C/min. Flood (4) with the intruding temperature as TMA
) Glass transition temperature (Tg) (DSC method) Temperature increase rate lO℃/mfn using DSC-20 manufactured by SEIKO Electronics Co., Ltd.
Measured with rounded caps anti-tachisho 1 (test piece A) with ethylene, 1, 4. 5. 8-dimethano-1.
2, 3, 4. A random copolymer (ethylene content -62 mol%) with 4a, 5,8,8a-octahyde-naphthalene (DMON), and has an intrinsic viscosity of 0. 47dl/a Glass transition point is 137℃, M
Using pellets of a cyclic olefin random copolymer having an FR260oC of 35 g/min and a softening temperature of 148°C, injection molding was performed under the following conditions to obtain a 120xl30x
A square plate of 2t@m was made and a nine-sided injection molding machine was used. IS-50EP manufactured by Toshiba Machine Cylinder temperature ZSO℃ Mold temperature 80℃ Injection pressure Primary/Secondary = 1000/800kg
/ cm2 Injection speed: medium speed This square plate is designated as test piece A.

(Test piece B) 3.4 kg of a cyclic olefin random copolymer pellet was prepared, and this copolymer was mixed with ethylene and 1,4
．． 5. 8-dimethano-1. 2, 3, 4, 4
a, 5, 8. 8a-octahydronaphthalene (
DMON), and the ethylene content in this copolymer is 66 mol%. The intrinsic viscosity [η] of this copolymer is 0. 6 di/
i The glass transition temperature is 122°C, the MFR2600C is 15 g/min, and the softening temperature is 138°C.

Separately, 0.6 kg of ethylene-propylene random copolymer pellets with an ethylene content of 80 mol% as a low-crystalline a-olefin copolymer were prepared, and the intrinsic viscosity of this copolymer was 2. The 2di/i glass transition temperature is 54°C and the MFR230-C is 0.7g/min.

After thoroughly mixing the above two types of belefts, the cylinder temperature was 2.
Melt the blended fox at 20°C and make it into pellets using a pelletizer. Using the obtained pellets, injection molding was performed under the same conditions as when producing the above test piece A.
A square plate of - is prepared and this square plate is designated as test piece B.

(Test piece C) Verhexin 2 5 B'' was added to 1 kg of pellets made of the cyclic olefin random copolymer and low crystalline a-olefin copolymer used in the production of test piece B.
(manufactured by NOF) and 3 g of divinylbenzene were thoroughly mixed. The mixture was melted using a twin-screw extruder at a cylinder temperature of 230°C, and reacted, and then pelletized using a beletizer. A square plate of 120Xl3oxzt was produced by injection molding under the same conditions as in the production of test piece A using the pellet thus prepared, and this square plate was designated as test piece C.

(Test piece D) 3.0 kg of the cyclic olefin random copolymer used in molding test piece A and nylon 6 (Toray M!.C)
M1017) 1. 5 kg and 0.5 kg of a modified cyclic olefin random copolymer modified with maleic anhydride prepared by the method below were thoroughly mixed, and the mixture was melted at a cylinder temperature of 250°C using a twin-screw extruder. The pellets were pelletized using a pelletizer, and injection molding was performed under the same conditions as when producing test piece A to produce a square plate with 120 x 130 x Zt axes.This square plate was used as test piece D. do.

Mixing preparation: 50 kg of maleic anhydride was added to 5 kg of pellets of ethylene/DMON random copolymer prepared when producing test piece A.
g (dissolved in 25 g of acetone), Verhexin 2 5
After adding 3 g of BT'' (manufactured by NOF ■) and mixing thoroughly, the cylinder temperature was set at 250°C using a twin-screw extruder to carry out the reaction while melting, and the resulting reaction raw material was transferred to a beletizer. The maleic anhydride content of the resulting resin was 0.8% by weight. Prepare the adhesive by dissolving 10g of Next, place the two test pieces so that the adhesive-applied surfaces face each other, overlap the two test pieces so that the adhesive area is 12.5 x 25 cm, and fix them using clips. After standing at room temperature for 30 minutes, the tensile shear adhesive strength was measured using a tensile tester.The tensile speed in this test was 50 speeds/min.

The results are shown in Table 1.

Adhesion was performed in the same manner as in Example 1, except that test pieces B, C, and D were used as shown in Table 1 instead of test piece A, and then the tensile shear strength was measured. The results are shown in Table 1.

Bonding amount 1'' Example 1, except that the adhesive was prepared by using dichloroethane instead of toluene. Bonding was performed in the same manner as in Example 1, except that this adhesive was used. Then, the bow shear strength was measured, and the results were as follows. are shown in Table 1.

Claims (1)

[Claims] (1) At least one solvent selected from the group consisting of aromatic hydrocarbon solvents, alicyclic hydrocarbon solvents, and halogenated hydrocarbon solvents, and the following formula [I] for 100 ml of the solvent: Ring-opening polymers or ring-opening copolymers formed by ring-opening polymerization of the cyclic olefins represented by the above, hydrogenated products thereof, copolymers of ethylene and a cyclic olefin represented by the following formula [I], and these. At least one type of cyclic olefin polymer selected from the group consisting of modified polymers of 0.
The following formula [ characterized by containing in an amount of 001 to 100g
A ring-opening polymer or ring-opening copolymer obtained by ring-opening polymerization of a cyclic olefin represented by [I], a hydrogenated product thereof, a copolymer of ethylene and a cyclic olefin represented by the following formula [I], At least one selected from the group consisting of modified products of these polymers, ring-opened polymers, ring-opened copolymers, hydrogenated products, copolymers, or compositions of modified products of these polymers and other resins. Adhesive for one type of cyclic olefin resin or cyclic olefin resin composition; ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, n is 0 or 1, m is 0 or is a positive integer, and R^1 to R^1^8 each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R^1^5 to R^ 1^8 may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond, and R^1^ 5 and R^1^8 or R^1^7
and R^1^8 may form an alkylidene group).