JPH01242647A - Chlorinated ethylene copolymer mixture - Google Patents

Abstract

PURPOSE:To obtain the title mixture which is excellent in crosslinkability and can give a crosslinked product excellent in ozone resistance, flame retardancy, mechanical strengths, etc., by adding an organic peroxide to a product of chlorination of a specified copolymer of ethylene with an alpha,beta-unsaturated dicarboxylic acid (anhydride). CONSTITUTION:Ethylene is mixed with an alpha,beta-unsaturated dicarboxylic acid (anhydride) (e.g., maleic anhydride) (the comonomer rate of the latter being 0.5-25mol.%) and, optionally, at most 25mol.% at least one monomer selected from among an unsaturated carboxylic ester, an alkoxyalkyl acrylate and a vinyl ester, and the obtained mixture is copolymerized to obtain an ethylene copolymer of a melt flow index of 0.1-100g/10min. This copolymer is chlorinated to obtain a chlorinated ethylene copolymer of a chlorine content of 5-40wt.% and a Mooney viscosity >=5 (at 100 deg.C). 100 pts.wt. this copolymer is mixed with 0.1-10.0 pts.wt. organic peroxide and, optionally, a crosslinking agent, a mercaptotriazine compound, a metal compound, etc., at, preferably, 70 deg.C or below.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a chlorinated ethylene copolymer mixture with excellent vulcanizability. More specifically, it not only has excellent cross-linking properties, but also good oil resistance, acid resistance, and alkali resistance, as well as good flexibility and compression set, and is suitable for metals and synthetics! This invention relates to a chlorinated ethylene copolymer mixture that has excellent adhesion to male substrates and good heat resistance.

(Prior art) Chlorinated polyethylene, especially non-grade chlorinated polyethylene rubber, has a chemically saturated structure and is a chlorine-containing polymer substance, so its crosslinked product (vulcanized product) is Because of its good physical properties such as weather resistance, flame retardance, chemical resistance, electrical properties, and heat resistance, it is suitable for wire coating, electrical parts,
It is used in a wide range of industrial fields, being molded into hoses, building materials, automobile parts, packing, sheets, etc.

[Issues that are initiated or attempted to be resolved]

However, unlike general-purpose rubber (for example, rubber whose main component is tutadiene), this chlorinated polyethylene has a chemically saturated structure as described above, so it is vulcanized using a vulcanizing agent such as sulfur, yellow, or sulfur donor. It is difficult to sulfurize. Therefore, a method of crosslinking using an organic peroxide as a crosslinking agent is generally used. However, is it possible to obtain a mixture with excellent heat resistance and compression set by crosslinking using an organic peroxide? The disadvantage of this method is that it has poor crosslinking efficiency and requires a large amount of organic peroxide and a crosslinking aid, leading to an increase in cost. Furthermore, the adhesion to metal or synthetic jam (for example, nylon or polyester fiber a) substrates is also poor.

From the above, the present invention does not have these drawbacks (problems), that is, it not only has extremely good vulcanizability, which is desired in the field of chlorinated polyethylene, but also allows the addition of a small amount of organic peroxide. As a result, it not only has excellent mechanical properties such as high heat resistance and high compression set, but also has good adhesion to metal and synthetic fiber base materials, and is required at low cost. The object of the present invention is to obtain a chlorinated ethylene copolymer mixture having satisfactory properties.

(Means and effects for solving the problems) According to the present invention, these problems can be solved by (A) melt flow index (JIS K7211, measured under conditions 4, hereinafter referred to as r MFRJ). 0.1~100g/
10 minutes, and the copolymerization ratio of α, β-unsaturated dicarboxylic acid and its anhydride is 0.5 to 25 mol% as a total layer. It is a chlorinated product of an ethylene copolymer with an anhydride, and the chlorine content of the chlorinated product is 5 to 4.
0% by weight, and Mooney viscosity (ML, 100°C)
The problem is solved by a chlorinated ethylene copolymer mixture consisting of 100 parts by weight of a 111 chemically modified tyrene copolymer which is 1+4 or 5 or more, and (B) 0.1 to 10.0 parts by weight of an organic peroxide. I can do it. The present invention will be specifically explained below.

(A) Chlorinated ethylene copolymer In producing the chlorinated ethylene copolymer used in the present invention, the raw material ethylene copolymer is mixed with at least ethylene and [α,β-unsaturated dicarboxylic acid and/or or its anhydride" (hereinafter referred to as "comonomer (1)"). The copolymer may be a copolymer of ethylene and comonomer (1), and in addition to ethylene and comonomer (1), a third copolymer component consisting of "unsaturated carboxylic acid ester, alkoxyalkyl acrylate, and vinyl ester" may be used. 1,000 members having at least one type of double bond selected from the group" [hereinafter "
It may also be a multi-component copolymer consisting of "comonomer (2)".

Among the comonomers (1), the α,β-unsaturated dicarboxylic acid usually has at most 20 carbon atoms, especially 4 to 1 carbon atoms.
Six pieces are preferred. Typical examples of the dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and 3,6-nintomethylene-1,2,3,6-titrahydroshisuphthalic acid (nadic acid@).

Among the α, β-unsaturated dicarboxylic acid components of the present application, the α
, anhydrides of β-unsaturated dicarboxylic acids are preferred, and maleic anhydride is particularly preferred.

Among the comonomers (2), the unsaturated carboxylic acid ester usually has 4 to 40 carbon atoms, and preferably 4 to 20 carbon atoms. As typical examples, those having good thermal stability such as methyl (meth)acrylate and ethyl (meth)acrylate are preferred.

Furthermore, the alkoxyalkyl acrylate usually has at most 20 carbon atoms. In addition, it is preferable that the alkyl group has 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms),
Furthermore, the alkoxy group has 1 to 8 carbon atoms (preferably,
1 to 4) is preferable. Representative examples of preferred alkoxyalkyl acrylates include methoxyethyl acrylate, ethoxyethyl acrylate and butoxyethyl acrylate.

Furthermore, the number of carbon atoms in vinyl ester is generally at most 2.
0 (preferably 4 to 16). Representative examples of suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butylene-1, vinyl biparate, and the like.

In the ethylene copolymer of the present invention, the comonomer (1
) copolymerization ratio is 0.5 to 25 mol%, and 1.0 to 25 mol%.
It is preferably 25 mol%, particularly preferably 1.0 to 20 mol%. Copolymerization ratio of comonomer (1) or 0.1 mol%
If less than 20% of the ethylene copolymer is used, the effect of the resulting chlorinated product will not be exhibited.

On the other hand, ethylene copolymers containing more than 25 mol % pose problems in terms of cost and production when industrially produced.

In the present invention, the terpolymer consisting of ethylene, comonomer (1) and comonomer (2) can be easily reacted without blocking during chlorination. Furthermore, the obtained chlorinated ethylene copolymer is preferred because it has excellent rubber elasticity and heat resistance.

In addition, the proportion of comonomer (2) is generally at most 25 mol% from the viewpoint of production and cost, and 0.
5 to 25 mol% is desirable, especially 120 to 2
5 mol% is preferred.

The VFR of the ethylene copolymer is 0.1 to 100 g/1
0 minutes, O,Sm2O3g/10 minutes is preferable, and 1.0 to ioo [710 minutes is particularly preferable. If an ethylene copolymer with an MFR of less than 0.1 g/10 minutes is used, the moldability and kneadability of the resulting chlorinated ethylene copolymer will not be good. On the other hand, 100 g/
If you use an ethylene copolymer that has been used for more than 10 minutes,
The mechanical properties of the resulting chlorinated ethylene copolymer are poor.

To produce the chlorinated ethylene copolymer of the present invention, the ethylene copolymer is suspended in an aqueous medium. In order to maintain this aqueous suspension state, it is preferable to add a small amount of emulsifying agent or suspending agent. At this time, radical generators such as benzoyl peroxide, azobisisobutyronitrile and hydrogen peroxide, antifoaming agents such as light silicone oil, and other additives may be added as necessary.

In producing the chlorinated ethylene copolymer of the present invention, it is preferable to chlorinate the aqueous B leakage using the following three methods.

The first method is to reduce the total chlorination amount by at least 25 °C below the melting point of the ethylene copolymer used in the first step or at a temperature higher than 50 °C.
60% of the ethylene copolymer is chlorinated, and the remaining chlorine is chlorinated in the second stage at a temperature 10°C or more higher than the chlorination temperature in the first stage or 5 to 15°C lower than the melting point of the ethylene copolymer. This is a method of doing so. □ The second method also involves chlorinating 20-60% of the total chlorination amount at a temperature at least 50C lower than the melting point of the ethylene copolymer used in the first step or at a temperature higher than 50C. In the second step, the temperature is raised to 1 to 7°C higher than the melting point of the ethylene copolymer, and at this temperature 1O-6(
), and in the third step, the remaining chlorination is carried out at a temperature 2 to 25°C lower than the melting point of the ethylene copolymer.

Additionally, the third method is to reduce 20 to 60% of the total chlorination amount at a temperature at least 25 °C below the melting point of the ethylene-based copolymer used in the first step or at a temperature above 50 °C. In the second stage, the humidity is 10°C higher than the chlorination temperature in the first stage, but 5-15°C higher than the melting point of the ethylene copolymer.
at least 30% of the remaining chlorination amount at low temperature;
By this stage, 60 to 90% of the total 111 elementation amount is chlorinated, and then in the third step, chlorination is carried out at a temperature lower than the melting point of the ethylene copolymer, or at a temperature lower than the melting point by 2°C or less. This is a method of doing this.

The chlorine content of the chlorinated ethylene copolymer used in the present invention obtained in this way is 5 to 45% by weight (
Preferably 5-40% by weight, preferably 10-35%
weight%). If the chlorine content of the chlorinated ethylene copolymer is less than 5%, there will be problems in recovering and purifying the resulting chlorinated ethylene copolymer. On top of that, #Flameability is poor. On the other hand, when the amount exceeds 45% by weight, the chlorinated ethylene-based co-polymers produced are unfavorable because their thermal stability and heat resistance are significantly reduced.

The Mooney viscosity is 5 points or more in a large rotor at a temperature of 100 DEG C., preferably 5 to 150 points, particularly preferably 10 to 150 points.

Additionally, the melt flow index its -7210
(hereinafter referred to as rFRJ)
is generally 1 to 100 g/10 minutes, and 3 to 5
0 g/10 minutes is preferred, particularly 5 to 30 g/10 minutes.

(B) Organic peroxide There are no particular limitations on the organic peroxide used in the present invention; it is particularly desirable that the organic peroxide has a decomposition temperature (a temperature with a half-life of 1 minute) or 120°C or higher; Especially 14
A temperature of 0°C or higher is preferable.

Representative examples of suitable organic peroxides include: ketone peroxides such as 1,1-bis-tertiary-phthylperoxy-3,3,5-h-limethylcyclohexane, 2.5
-dimethylhexane-2; hydroperoxyl-1-12.5-dimethyl- such as 5-sivitro-oxide
Mention may be made of peroxy esters such as 2,5-cy tertiary-phthyl peroxyhexane, diacyl peroxides such as benzoyl peroxide, and dialkyl peroxides such as dicumyl peroxide.

Furthermore, polyfunctional substances such as triallyl cyanurate and triallyl isocyanurate, which are commonly used as crosslinking aids in the rubber field, may be blended.

Furthermore, by incorporating a mercaptotriazine compound described below, the tearability of the mixture at relatively high temperatures can be improved.

(C) Mercaptotriazine compound late mercap! -)-Ryazine compounds are used as vulcanizing agents or vulcanization accelerators in the rubber industry, and are represented by the general formula or the following formula (formula (I)).

(R is selected from the group consisting of a mercapto group and an amino group) In this formula (I), the amino group may have a hydrocarbon group having at most 20 carbon atoms. .

Representative examples of this mercaptotriazine compound include:
1,3,5-trithiocyanuric acid, 1-hexylamino-3,5-dimethylcaptotriazine, 1-diethylamino-3,5-dimercaptotriazine, 1-cyclohexylamino-3,5-simeflekabutotriazine, etc. can give. This compound was published in Japanese Patent Publication No. 59-1009.
It is described in detail in the specification of Publication No. 9.

In producing the composition of the present invention, the following metal compound may be blended as an acid acceptor in order to prevent dehydrochlorination.

(D) Metal Compounds Metal compounds include oxides, hydroxides, carbonates, carboxylates, silicates, borates and phosphites of metals in Group 1I of the Periodic Table, and metal compounds in Group 1I of the Periodic Table. Examples include oxides of Group 1 Va metals, basic carbonates, basic carboxylates, basic phosphites, basic subacid I%i salts, and tribasic sulfates.

Representative examples of the metal compounds include magnesium oxide (magnesia), magnesium hydroxide, magnesium carbonate,
Barium hydroxide, magnesium carbonate, barium carbonate, calcium oxide (quicklime), calcium hydroxide (slaked lime)
, calcium carbonate, calcium silicate, calcium stearate, calcium phthalate, magnesium phosphate, calcium phosphite, zinc oxide (zinc white), tin oxide,
Resurge, Red Lead, White Lead, Dibasic Lead Phthalate, 2ft4
Basic lead carbonate, lead stearate, basic lead phosphite, 11
! Basic silver phosphite, basic lead sulfite, tribasic lead sulfate, etc. can be used.

The average particle size of the metal compound is usually 0.1=100 μl, preferably 0.2 to 1.10 μl, particularly 085 μl.
~50 μm is suitable. If a metal compound with an average particle diameter of less than 0.1 μm is used, scattering may occur during kneading, causing problems in handling. On the other hand, Ion g, v
If a material exceeding A is used, secondary agglomeration is likely to occur, making it difficult to uniformly disperse the material.

(E) Mixing ratio: 4 to 100 parts by weight of the combined chlorinated ethylene system
The proportion of peroxide is a, 1 to +1), 0 weight ijE
0.5 to 10. Oji parts are desirable, and 0.5 to 8.0 tμ parts are particularly suitable. If the ratio of the organic peroxide to 100 parts by weight of the chlorinated ethylene copolymer is less than 0.1 part by weight, a mixture with excellent mechanical properties cannot be obtained. On the other hand) if the weight part exceeds λ of 0.0, there is a problem in terms of flexibility.

Furthermore, when blending 1 to riazine compounds to Mercap 1, the mixing ratio is generally at most 2,0;'747 to 100 parts by weight of the chlorinated ethylene copolymer.
It is preferably 0, DI-2.0 parts by weight, preferably 0.02 to 1.5 parts by weight, particularly 0.1 to 1 parts by weight.
．． 21 parts by weight is suitable. 2 parts by weight of mercaptotriazine compound per 100 parts by weight of chlorinated ethylene copolymer
．． If more than 0 parts by weight is added, crosslinking or rather deterioration will occur.

Furthermore, when a metal compound is mixed, the mixing ratio is generally at most 15. Oti part, 1.0~15
．． Preferably 0 parts by weight, 2.0~15゜0 parts by weight♀
Preferably, 3.0 to 12.0 parts by weight is especially suitable. 15. Even if it is blended in an amount exceeding the amount of Oi, it is not only impossible to further prevent the dehydrochlorination reaction, but also the processability deteriorates, and the rubber strength of the resulting crosslinked product decreases.

(F) Mixing method, molding method, etc.Although the mixture of the present invention can be obtained by uniformly blending the above-mentioned substances, there is also a filler 1 dehydrochlorination inhibitor commonly used in the rubber industry and resin industry. Additives such as plasticizers, oxygen, ozone, heat and light (UV) stabilizers, lubricants and colorants may be added depending on the intended use of the mixture.

When producing the mixture of the present invention, the blending (mixing) method may be to use a mixer commonly used in the art such as an oven roll, a trifrelter, a Banbury mixer, and a Nigoo mixer. .

Among these mixing methods, two or more of these mixing methods may be applied in order to obtain a layer-uniform mixture (for example, after mixing in a trifrelter, the mixture may be rolled in an oven roll, etc.). method of mixing). In these mixing methods, if melt-kneading is carried out at a relatively high temperature, some or all of the chlorinated ethylene copolymer used may be crosslinked. For this reason, it is usually necessary to carry out the process at 70°C or lower.

The mixture of the present invention may be molded into a Tasto seal using molding machines commonly used in the rubber industry, such as extrusion molding machines, injection molding machines, compression molding machines, and calender molding machines. Also. A desired shape can be obtained by adding a chlorinated ethylene copolymer or a mixture such as those mentioned above to produce a molded product while crosslinking, which is a method commonly used in the rubber technology field, in which crosslinking and molding proceed simultaneously. It may be molded into a desired shape using a molding machine such as an extrusion molding machine, an injection molding machine, a compression molding machine, or a calender molding machine.

(Examples and Comparative Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, in Examples and Comparative Examples, tensile strength (r
TJ) and elongation (hereinafter referred to as "EB") were measured using a Schober tester.

Further, the hardness test was performed using a Shore A hardness meter. Furthermore, the compression set test was performed by compressing to 25% compression.
After maintaining compression under a constant load, it was left in a heating tester at 100°C for 22 hours. Thereafter, the load was removed, and the sample was allowed to stand in a constant temperature room at 23°C and 60% humidity for 30 minutes, and its strain rate was measured. In addition, the crosslinking test was performed using a disk rheometer (ODR-100 model) at a temperature of 170°C, an amplitude of 3 degrees, a full scale of 100 g/
am'' for 1 hour, and the crosslinking curve at that time was measured.

Furthermore, the heat resistance test was carried out by leaving the pieces at a temperature of 130° C. for 70 hours and 120 hours, respectively, and measuring the residual tensile elongation (elongation rate) at JIS 6301.

In addition, the tear property test was conducted according to JIS 6301.
Measurements were made using SB type dumbbells in a constant temperature room at a temperature of 23° C. and a relative humidity of 60%. Also.

Approximately 1-) was adhered and evaluated by peeling in a 90 degree direction at a tensile speed of 50 mm according to JIS K6:1 old.

The types and physical properties of the chlorinated ethylene copolymers, organic peroxides, crosslinking aids, and mercaptotriazine compounds used in Examples and Comparative Examples are shown below.

((A) Chlorinated ethylene copolymer) As a chlorinated ethylene copolymer, VF
R? 00g71.0min-C and melting point 103℃
Ethylene-methyl methacrylate-1/-maleic anhydride terpolymer (copolymerization ratio of methyl methacrylate-1/: 18.5 mol%, copolymerization ratio of maleic anhydride: 1)
5 mol%, hereinafter referred to as rEMMAJ), and chlorinated the core copolymer at a temperature range of 50 to 85°C with stirring until the chlorine content of the core copolymer reached 15.2% by weight. one-step chlorination). Then, the reaction system was
The temperature was raised to 9 to 118°C, and in this temperature range, the introduction of chlorine was stopped and annealing was performed for 30 minutes (second stage annealing). Then, the reaction system was cooled and 88-
In the temperature range of 106 °C, the chlorine content is 35.1% by weight, and the resulting Mooney viscosity (ML, 10D °C) is 32.5. ! Hydrogenated ethylene l+4-based copolymer (FR10, 2g/10 min, hereinafter T r (
:IEMMA(A)'') and the said EMMAIO.
Prepare g in the same manner as above, and heat to 50-80℃ while stirring.
The chlorine content of the copolymer in the temperature range of 8.1 months
% by weight (first stage chlorination). The reaction system was then heated to 93-103°C and chlorinated in this temperature range until the chlorine content was 30.0% by weight (second stage chlorination), and then in the temperature range of 118-120°C. chlorination until the chlorine content was 35.1% by weight (third stage chlorination), Mooney viscosity (ML, +4°10
0°C) or 34.5 chlorinated ethylene copolymer (F
R10,8g / 10 minutes, hereafter r CIEMMA (B
) J) was used.

((1'l) Organic peroxide) Dicumyl peroxide (hereinafter r
DCPJ) was used.

[(C) Crosslinking aid]

In addition, triallylisocyanurate (
Hereinafter referred to as rTAIcJ) was used.

((D) Mercaptotriazine compound) Furthermore, 1,3.5-mercapto-3-triazine (hereinafter referred to as F "asin") was used as a mercaptotriazine compound.

((E) Metal compounds) In addition, as metal compounds, magnesium oxide (hereinafter referred to as rMg0J) with an average particle size of 1.0 ILm and red lead (hereinafter referred to as ``Pb3O4'') with an average particle size of 1.5 gm are used.
”) was used.

Examples 1 to 6, Comparative Examples 1 to 8 The formulations shown in the amounts and types shown in Table 1 were kneaded at room temperature (approximately 20°C) for 20 minutes using oven rolls to form sheet-like products. did. Each of the obtained sheets was crosslinked using a compression molding machine at a temperature of 175°C and a pressure of 200 kg/cm for 10 minutes to produce a crosslinked product. The resulting crosslinked product was tested for tensile strength, elongation, hardness, compression set, heat resistance, and tearability. The results are shown in Table 2. Furthermore, the crosslinking test was carried out using a sheet material obtained by oven rolls. The results are shown in FIG.

(Left below) Comparative Example 9 Instead of CIEMMA (A) used in Example 1, CIEMMA (A) with an approximate molecular weight of approximately 200,000 and a density of 0.
Mooney viscosity (MS, 100 °C) obtained by chlorinating high-density polyethylene with a density of 950 g/cm" by an aqueous suspension method is 60, and the chlorine content is 35.2% by weight. A sheet was molded by kneading in the same manner as in Example 1, except that chlorinated polyethylene was used.The obtained sheet was crosslinked in the same manner as in Example 1 to produce a crosslinked product. Strength, elongation, hardness, compression set, heat resistance and tearability tests were conducted.The results are shown in Table 2.Furthermore, a vulcanization test was conducted in the same manner as in Example 1.The results are shown below. Shown in Figure 1.

(Hereinafter, blank spaces) In Comparative Examples 4 and 5, dehydrochloric acid removal occurred during crosslinking, and it was not possible to form a sheet-like crosslinked product.

In addition, an adhesion test was conducted on each of the chlorinated ethylene-based residual ball coalescence mixtures obtained in all Examples.

In each case, specimens of chlorinated ethylene copolymer mixtures were cut.

Furthermore, the crosslinking curves of the mixtures (kneaded products) obtained in Examples 1 and 4 and Comparative Examples 1 and 9 are shown in 1st [-, A as a, b, c, and d, respectively.

From the results of the above Examples and Comparative Examples, the crosslinking properties obtained by the present invention are 11t! It is clear that the hydrogenated ethylene copolymer mixture not only has excellent tensile strength (T), compression set, and heat resistance, but also has an excellent crosslinking curve when viewed from the rheometer curve. .

(Effects of the Invention) As is clear from FIG. 1, the chlorinated ethylene residual hair coalescing mixture obtained by the present invention not only has superior crosslinking properties compared to ordinary chlorinated polyethylene, but also has the following effects. Demonstrate.

(1) #Good ozone properties.

(2) Excellent repellency.

(3) It also has good flame retardancy.

(4) Excellent weather resistance and durability.

(5) Tearability and other mechanical strengths are also good.

(6) Excellent oil resistance.

(7) Furthermore, #thermal properties and low temperature properties are also good.

(8) Excellent adhesion to metals, etc.

The mixture of chlorinated ethylene and chlorinated ethylene has excellent properties as shown in L, and can be used in a wide variety of fields. Typical application examples are shown below.

(1) Various parts for automobiles (e.g. ports, chew materials) (2) Covering materials for heavy wires (3) Adhesives (4) Parts for electronic equipment and upper air equipment

[Brief explanation of the drawing]

FIG. 1 is a crosslinking curve diagram of each mixture prepared in Examples 1 and 2 and Comparative Examples 1 and 8, measured using a disc rheometer. In this figure, the vertical axis shows torque (Kg-C11), and the horizontal axis shows crosslinking time (Kg-C11).
minutes). In addition, a, b. c and d show the crosslinking curves of the mixtures obtained in Example 1, Example 2, Comparative Example 1 and Comparative Example 8, respectively.

Claims (1)

[Claims] (A) Melt flow index is 0.1 to 100 g/
10 minutes, and the total copolymerization ratio of α, β-unsaturated dicarboxylic acid and its anhydride is 0.5 to 2.
It is a chlorinated product of an ethylene copolymer of at least 5 mol% of ethylene and an α,β-unsaturated dicarboxylic acid and/or its anhydride, and the chlorine content of the chlorinated product is 5 mol%.
~40% by weight, and Mooney viscosity (ML_1_+
_4, a chlorinated ethylene copolymer mixture comprising 100 parts by weight of a chlorinated ethylene copolymer having a temperature of 5 or more (100°C), and (B) 0.1 to 10.0 parts by weight of an organic peroxide.