CN1116631A - Method for producing thermoplastic styrenic resin composition - Google Patents

Abstract

The invention relates to a process for preparing thermoplastic styrene resin composition with excellent ball drop impact resistance, high tensile strength, good processing formability and high gloss, which is characterized in that a carboxyl-containing high-molecular agglutinant is added into a synthetic rubber emulsion in a two-stage or more-stage adding manner in the aggregation process of the synthetic rubber emulsion.

Description

Method for producing thermoplastic styrenic resin composition

The existing polystyrene-based acrylonitrile-butadiene-styrene copolymer (ABS) resin manufacturing technology usually consists of rubber emulsion and styrene (SM), acrylonitrile (AN) or methyl methacrylate (MMA ) and other monomers undergo emulsion polymerization. And because of its good surface gloss and high resistance to falling ball impact, it is widely used in daily life such as auto parts and electrical appliances. Among them, the particle size of the rubber emulsion is related to the processing properties and impact resistance of the product, that is, the impact resistance strength increases when the particle size increases. When the particle size increases, the tensile strength and gloss decrease. Therefore, increasing the particle size of rubber latex to prepare impact-resistant resins while still maintaining high tensile strength and high gloss is an important topic for polymer researchers today.

The present invention discloses a manufacturing method to prepare a thermoplastic styrenic resin composition, which has the characteristics of aggregated particle size, excellent high ball impact resistance, good processability, high tensile strength and high gloss and other characteristics. The technology of rubber particle aggregation is one of the important topics that polymer researchers have been devoting to develop for many years. In the preparation method of rubber particle aggregation, there are: using acid anhydride technology (U.S.Pat.3652721, Dalton, etc.) or technology containing carboxylic acid (U.S.Pat.3944630, Fumio, etc.) are suitable for aggregated particle sizes in a narrow distribution range; techniques using pressurization or shearing (ISRC—U.K.Pat.976212, 297213, 976214 and 1039727) can be used for continuous operation to obtain a wide range of Agglomerative particle size distribution in a range; using hydrophilic polymers in the latex process as an aggregating agent for water-repellent elastomers (refer to Wesslaw et al. "Observation on the Aggregation of Polymer Lattice", "Inves-tigations into the Agglomeration of Polymer Latices", Ange-wandte Makaromolekulare Chemie, 2, No.20, Apr.30, 1969, PP.1-25), and (U.S.Pat.3825621, Ford, etc.) wherein the aggregation agent and the graft polymerization reaction conditions must be adjusted according to the product characteristics choose.

In the aggregation method of chemical methods such as adding acid, salt or solvent or physical methods such as pressurization in the above-mentioned U.S. patent, the adding speed and stirring speed may affect the particle size, and the particle size is easy to be super large due to the difficult control of the conditions during the production period. Or clots, acids and salts will also partially destroy the stability of emulsification. Especially when adding aggregated rubber particles in one (segment) way to polymer coagulants containing carboxylic acid groups (hereinafter referred to as C.A.latex), usually only a fairly narrow particle size distribution is obtained, which may be difficult for the high-impact resin to be manufactured. The increase in particle size leads to a decrease in tensile strength and gloss. However, when using the existing method of continuously adding C.A.latex to aggregate rubber particles (the addition time is more than 5 minutes), the particle size distribution is not easy to control, so that it is impossible to make graft structures for various particle sizes during graft polymerization. Graft adjustment, resulting in uncontrollable graft polymerization ratio, resulting in poor physical properties. For ABS resin with small particle size, because the particle dispersion distance in the resin is shorter than that of large particle rubber of the same weight, it is easy to cause bad aggregation of rubber particles due to melting and shearing during processing and molding. On the contrary, the falling ball impact strength of the finished product is reduced. Especially during high-temperature injection molding, the surface gloss of molded products is significantly reduced due to poor aggregation of rubber particles.

In order to solve the above problems that it is difficult to obtain thermoplastic resins with impact resistance, high tensile strength and high gloss, the present invention develops a novel manufacturing method through dedicated research results, that is, to use C.A.latex in a specific ratio and a specific time interval Add two or more stages to aggregate rubber particles, so that the proportion of graft polymerization is easy to control, and obtain excellent high falling ball impact, high tensile strength, good processability, and high gloss thermoplastic styrene Resin composition.

Unless otherwise specified, the parts by weight of the synthetic rubber emulsion or C.A.latex described below are all expressed in dry weight state. This manufacturing method is characterized in that:

(1) Add 1.0 to 6.7 parts by weight of C.A.latex to 100 parts by weight of synthetic rubber emulsion to implement aggregation, and the pH value of the emulsion after aggregation is not less than 6;

(2) C.A.latex adopts two or more stages of addition to gather rubber particles, and the time interval between the first stage and the second stage of C.A.latex addition is 10 to 60 minutes; wherein: (a) for 100 parts by weight of rubber, The addition amount of C.A.latex in the first section is 0.2-0.8 parts by weight; (b) for 100 parts by weight of rubber, the sum of the addition amount of C.A.latex after the first section is 0.8-5.9 parts by weight; (c) the addition amount of the first section and the first section The ratio of the total amount of C.A.latex added after a period is 1:1 to 1:20;

(3) In the presence of 100 parts by weight of the aggregated rubber emulsion, two or more monomers can be selected from aromatic vinyl monomers, unsaturated nitrile monomers, and methacrylate monomers. 10 to 150 parts by weight of monomers, and 0 to 50 parts by weight of unsaturated group-containing monomers that can be copolymerized with the aforementioned monomers are grafted and polymerized to form the characteristic composition of the present invention.

The present invention is for the manufacture method of this characteristic composition, according to its reaction step its feature is described in detail in the back respectively:

1. Preparation of synthetic rubber latex

The synthetic rubber emulsion used in the production method of the present invention includes polybutadiene-based and acrylate-based homopolymers, or copolymers, terpolymers, and polymer rubbers that can be formed with these monomers. For example, polybutadiene, polybutyl acrylate and butadiene-unsaturated aliphatic compound monovinyl copolymers, such as butadiene-styrene, butadiene-α-methylstyrene, etc. ; Butadiene-unsaturated nitrile copolymers, such as butadiene-acrylonitrile, butadiene-methacrylonitrile, etc.; butadiene-acrylate copolymers, such as butadiene-methyl acrylate , Butadiene-n-butyl acrylate copolymer; butadiene-methacrylate copolymer, such as butadiene-ethyl methacrylate. The rubber particles in the synthetic rubber emulsion are usually between 0.04 and 0.18 μm.

Two. Preparation of C.A.latex

The C.A.latex of the present invention generally comprises a copolymer of carboxycarboxylic acid monomers and alkyl acrylate monomers. Alkyl carboxylic acid monomers can be acrylic acid, methacrylic acid, 2-methylene succinic acid, crotonic acid and the like. Whereas the alkyl acrylate monomers include: methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and the like.

Appropriate emulsifiers can also be added to the reaction of this step, such emulsifiers include anionic surfactants such as sodium salts of fatty acids, potassium salts of fatty acids, sodium alkylbenzenesulfonate, sodium rosinate, phenylethoxysulfonate salts and similar compounds.

When the base rubber latex of the present invention is aggregated by C.A.latex, the base rubber particles only need to mix and stir the two latexes at room temperature to achieve the aggregation effect.

If the pH value of C.A.latex is less than 4, there will be no significant aggregation effect. When mixed with rubber latex, the pH value is not less than 6, preferably between pH 7 and 13. When the pH value is less than 6, a good aggregation effect cannot be obtained, and when the pH value is higher than 13, the aggregated rubber latex is unstable.

3. Aggregation reaction

The addition amount of C.A.latex in the first stage to 100 parts by weight of rubber is 0.2-0.8, and 0.3-0.6 is the best; when the addition amount of the first stage is less than 0.2, it is similar to the one-stage addition method and cannot be used at high rubber content. A high-gloss resin is obtained. When it is higher than 0.8, super-aggregated particles will be generated, which will reduce the tensile strength. The total amount of C.A.latex added to 100 parts by weight of rubber after the first stage is 0.8 to 5.9, and 1 to 3 is the best; when the total amount added after the first stage is less than 0.8, a resin with high falling ball impact cannot be obtained , when it is higher than 5.9, the formability of processing will be deteriorated, which will cause uneconomical production cost.

In the present invention, each addition of C.A.latex needs to be completed within 3 minutes, preferably within 1.5 minutes, more preferably within 30 seconds. Moreover, the time interval between the first stage and the second stage of adding C.A.latex is 10 to 60 minutes, and 20 to 40 minutes is the best; The surface gloss becomes extremely poor during molding, and there is no further improvement in gloss and falling ball impact for more than 60 minutes. Moreover, the rubber particles aggregated by the method of the present invention have an average particle diameter between 0.23 and 1.00 μm.

4. Graft polymerization reaction

The preparation of graft copolymers usually uses the existing graft polymerization technology to carry out graft polymerization reactions with monomer mixtures in the presence of aggregated elastomers (rubbers), using chemical combination or grafting of at least one polymer on the elastic body. According to the ratio of the monomer to the elastomer and the polymerization conditions, the polymer grafted on the elastomer to the desired degree of grafting can be obtained at the same time. Usually, in the graft polymerization reaction, the polymerization conditions, the chemical properties and particle size of the elastomer, the rate of monomer addition, the chain transfer agent, the catalyst, etc. are all affected.

The initiator or catalyst is usually in the range of 0.01 to 5.0 parts by weight of the polymerizable monomer, preferably 0.1 to 3.0 parts, depending on the monomer and the desired polymerization reaction. Initiator can be added incrementally to facilitate graft polymerization.

The molecular weight of the grafted polymer can be controlled by the temperature during the graft polymerization, and/or a relatively small amount of existing molecular weight regulators, such as mercaptans, halides and terpenes, etc. (for example: positive twelve Alkylthiol, tertiary (dodecyl) mercaptan and terpinolene) to regulate. Graft polymerization can also be controlled by varying the amount of polymer grafted onto the elastomer (rubber). In general, this effect can be achieved by continuously or incrementally adding the monomer mixture to the polymerization reaction, preferably simultaneously with the continuous or incrementally adding the initiator. Various existing emulsified radical polymerization initiators can be used in graft polymerization, including existing peroxides and azo compounds, which can be added at one time or continuously or incrementally during graft polymerization to join. Suitable peroxide initiators, for example alkali metal peroxides, persulfates, perborates, peracetates, percarbonates, hydrogen peroxide. In addition, oil-soluble initiators can also be included, such as bis-tert-butyl peroxide, benzoyl peroxide, lauryl peroxide, oleyl peroxide, toluyl peroxide, bis-perphthalic acid-tert Butyl ester, tert-butyl peracetate, tert-butyl perbenzoate, cumyl peroxide, tert-butyl peroxide, isopropyl peroxy dicarbonate, 2,5-dimethyl- 2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)-hexane-3, tert-butylated Oxyhydrogen, p-Cymene Hydroperoxide, p-Methylated Hydroperoxide, Cyclopentylated Hydroperoxide, Diisopropylbenzene Hydroperoxide, p-Tert-Butyl Isopropyl Hydroperoxide, Pinane hydroperoxide, 2,5-dimethylhexyl-2,5-dihydroperoxide, etc., or a mixture of the above. Other forms of free radical catalysts have also been used, such as actinic irradiation.

The aggregated rubber emulsion and monomer mixture are stirred under an inert gas with a temperature range of 20-100°C for polymerization, or pressurized to 0-100 p.s.i.g. The polymerization is continued until at least 90% of the monomers are polymerized. The polymerization time usually takes 2-10 hours, and preferably 4-8 hours. Finally, residual monomers and other volatile compounds are separated by dehydration, washing, and drying. Latex can be spray dried, coagulated with salt, or otherwise dehydrated.

When the rubber emulsion after aggregation is carried out graft polymerization, in the presence of 100 parts by weight (dry weight), it can be obtained from aromatic vinyl monomers, unsaturated nitrile monomers, and methacrylate monomers. 10-150 parts by weight of two or more monomers are selected, and 0-50 parts by weight of monomers containing unsaturated groups that can be polymerized with the aforementioned monomers are used for graft polymerization.

Aromatic vinyl monomers can be: styrene, α-methylstyrene, α-chlorostyrene, p-t-butylstyrene, p-methylstyrene, o-chlorostyrene, p-chlorostyrene , 2,5-dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-tribromostyrene, 2,5-dibromostyrene, etc., in which styrene or α-methylbenzene Ethylene is preferred.

The unsaturated nitrile monomers can be: acrylonitrile, α-methacrylonitrile, methacrylonitrile, malononitrile, fumacronitrile, etc., among which acrylonitrile is preferred.

Methacrylate monomers can be: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, methacrylic acid Cyclohexyl ester, lauryl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate and dimethylaminoethyl methacrylate, among which methyl methacrylate is preferred.

Copolymerizable monomers such as maleimide monomers can be: maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide Laimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide Laimide, N-2,3- or 4-tolylmaleimide, N-2,3- or 4-ethylphenylmaleimide, N-2,3- or 4-butane Phenylmaleimide, N-2,6-tolylmaleimide, N-2,3- or 4-chlorophenylmaleimide, N-2,3- or 4-bromo Phenylmaleimide.

In addition to the above, other copolymerizable monomers include: acrylic monomers, anhydrous maleic acid, anhydrous methine succinic acid, anhydrous methylmaleic acid, anhydrous 25 Acids, unsaturated carbonic acids such as mono- and dihydroxy esters and their ester monomers, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinyl chloride, vinyl chloride Ethylene tetrafluoride, ethylene chlorotrifluoride, propylene hexafluoride, butadiene, propenylamine, isobutenylamine, vinyl acetate, vinyl azotriene, vinyl azotriene , Vinyl diaminocarbamide, vinyl ether, vinyl ketone, benzocyclopropene, naphthoethylene, etc.

5. Blending of polymers

The end product of the graft polymerization procedure in the process of the present invention is often a higher rubber content polymer mixture. Graft polymers are often mixed into copolymers of the aforementioned grafting monomers, such as styrene-acrylonitrile copolymers, styrene-methyl methacrylate copolymers, etc., to increase the amount of matrix polymer and reduce rubber content. Such resin copolymers used to dilute the graft copolymers can be produced via emulsification, suspension or bulk polymerization techniques. Typically, the final blend contains 2 to 50 weight percent of the rubber elastomer component, preferably 7 to 35 weight percent, and most preferably 10 to 25 weight percent.

The following examples can describe the superiority of the present invention in detail, but are not intended to limit the protection scope of the present invention, and the mentioned ingredients are based on parts by weight.

Embodiment 1-5

Five kinds of graft polymers obtained by adding C.A.latex in different ways are prepared according to the following steps (A)-(D):

(A) Manufacturing method of non-aggregated rubber latex (A-1) Composition parts by weight 1,3-butadiene 150.00 Potassium persulfate solution (1%) 15.00 Sodium Lauryl Sulfate Solution (10%) 20.00 distilled water 190.00 Ethylene glycol dimethacrylate 0.13

According to the above formula, react at a reaction temperature of 65° C. for 12 hours to obtain a rubber latex (A-1) with a conversion rate of 94%, a solid content of about 40%, and a weight average particle size of about 0.1 μm.

(B) Manufacturing method of CAlatex (B-1) Composition parts by weight ethyl acrylate 90.0 acrylic acid 10.0 Potassium persulfate solution (1%) 0.5 Sodium Lauryl Sulfate Solution (10%) 0.5 distilled water 200.0

According to the above formula, react at a reaction temperature of 75°C for 5 hours to obtain C.A.latex (B-1) with a conversion rate of about 95% and a pH of 6.0.

(C) The manufacture method of aggregation rubber latex (C-1) will contain the rubber latex (A-1) of 100 weight parts (dry weight), according to the C.A.latex (B-1) composition in Table 1 with two stages ( or above) to aggregate rubber particles, and the resulting aggregated rubber latex (C-1) has a pH value of about 8.5.

(D) Graft polymerization of the aggregated rubber latex (C-1) to produce a graft copolymer (D-1)

Composition parts by weight Aggregated polybutadiene latex (dry weight) 100.0 Styrene 75.0 Acrylonitrile 25.0 tertiary-dodecylmercaptan 2.0 Di-isopropylbenzene hydroperoxide 3.0 Ferrous sulfate solution (0.2%) 3.0 Sodium formaldehyde sulfoxylate solution (10%) 0.9 EDTA solution (0.25%) 3.0 Example 6

As in the experimental procedures of Examples 1 to 5, and the addition method of C.A.latex (B-1) is the same as in Example 1 (Table 1), except that the graft polymerization monomer in step (D) is changed to:

monomer parts by weight Styrene 70.0 Acrylonitrile 20.0 Methyl methacrylate 5.0 N-Phenylmaleimide 5.0

Under the continuous feeding of mixed monomers, the graft polymerization reaction was carried out for 8.5 hours, and a graft copolymer with a conversion rate of about 95% was obtained.

Table 1: CAlatex (B-1) addition method of Examples 1-6 Example Add method The amount added in the first paragraph (#) The amount added in the second paragraph (#) The amount added in the third paragraph (#) Total amount added (#) The interval between adding the first and second paragraphs (minutes) ratio(*) 1 two sections 0.3 2.2 0 2.5 20 7.3 2 two sections 0.4 2.4 0 2.8 20 6.0 3 two sections 0.4 2.4 0 2.8 40 6.0 4 two sections 0.6 2.2 0 2.8 20 3.7 5 Three sections 0.6 2.0 0.4 ($) 3.0 20 4.0 6 two sections 0.3 1.8 0 2.1 20 6.0

(#): The unit is parts by weight

(*): Total amount of C.A.latex after the second paragraph/C.A.latex amount in the first paragraph

($): The interval between adding the second and third paragraphs is 10 minutes

Comparative Examples 1-8

Unaggregated rubber latex (A-1), C.A.latex (B-1) and graft copolymer (D-1) were produced according to the same formulation as in Examples 1-6. Only C.A.latex is added in two stages (comparative examples 1-4), one stage or continuous (comparative examples 5-8) as shown in Table 2.

Table 2: Addition methods of CAlatex (B-1) in Comparative Examples 1 to 8 comparative example Add method The amount added in the first paragraph (#) The amount added in the second paragraph (#) Total amount added (#) The interval between adding the first and second paragraphs (minutes) Continuous adding time (minutes) ratio(*) 1 two sections 0.1 2.7 2.8 20 —— 27 2 two sections 1.0 1.8 2.8 20 —— 3 two sections 2.5 0.3 2.8 20 —— 4 two sections 0.4 2.4 2.8 5 —— 5 section —— —— 2.8 — —— 6 section —— —— 4.0 — —— 7 continuous —— —— 2.8 — 10 8 continuous —— —— 2.8 — 20

(#): The unit is parts by weight

(*): Total amount of C.A.latex after the second paragraph/C.A.latex amount in the first paragraph

Physical Performance Test

Add 5% sulfuric acid aqueous solution to the graft copolymer (D-1), and stir at 90°C for 10 minutes to obtain a condensed precipitate, which is dehydrated, washed with water, and dried to obtain a graft copolymer powder.

Add 2,6-di-tert-butyl-4-methylazole (0.1%), triphenyl phosphate (0.1%), ethylene bis stearamide (2%), etc. to the AS resin, and the above-mentioned grafting The copolymer powder is mixed into different rubber content, and after being mixed together, it is extruded by an extruder to obtain a plastic pellet product. Gloss and tensile strength physical test, the determination method is as follows:

Falling ball impact strength

Use an injection molding machine to inject a circular test plate with a radius of 50mm and a thickness of 3mm, and hit the center of the test plate with a 5kg steel ball at room temperature (23°C) to obtain the maximum energy that the test plate is not damaged. The unit is kg .cm. surface gloss

Using an injection molding machine (SM-90 injection molding machine manufactured by Chen Hsong Machinery Co., Ltd.) at molding temperatures of 230° C. and 280° C., a plate-shaped molding of 50 mm (width)×90 mm (length)×3 mm (thickness) was injected. The gloss meter (manufactured by Gardner, Micro-TRI type equipment) for the molded flat plate was 60. The average value of the five-component flat plate was determined by the incident angle, and the unit is %.

tensile strength

It is tested according to the US standard ASTMD-638 method, and its unit is kg/cm.

Test Results

(A) The graft copolymer obtained according to the different ways of adding C.A.latex in Examples 1-6, and then the test piece of the plastic particle product was subjected to the above physical test, and the results are shown in Table 3.

Table 3: Test results of falling ball impact strength, surface gloss and tensile strength of the plastic product test pieces obtained in Examples 1-6.

Example Rubber content (parts by weight) Falling ball impact strength (kg cm)   Surface Gloss   Tensile strength (kg/cm) Shot temperature 230℃ Shooting temperature 280℃ 1 20 400 92 82 402 2 20 400 93 80 406 3 20 420 90 82 395 4 20 380 91 80 390 5 20 380 88 78 386 6 20 380 90 80 390

It shows that by adding C.A.latex in two or more stages by the method of the present invention, an aggregated rubber-modified styrene resin with excellent high falling ball impact strength, high tensile strength and high gloss can be obtained.

(B) The graft polymers obtained by adding C.A.latex in different ways in Comparative Examples 1 to 8, and then the test pieces of plastic pellets were subjected to the above physical tests.

The results are shown in Table 4.

Table 4: Test results of falling ball impact strength, surface gloss and tensile strength of the plastic product test pieces obtained in Comparative Examples 1-8. Example Rubber content (parts by weight) Falling ball impact strength (kg cm) surface gloss Tensile strength (kg/cm) Shot temperature 230℃ Shooting temperature 280℃ 1 20 320 90 62 398 2 20 340 86 70 362 3 20 350 88 68 358 4 20 360 88 52 392 5 20 320 92 82 408 6 20 380 76 64 352 7 20 360 89 46 386 8 20 350 90 34 378

As shown in Table 4, when the amount of C.A.latex added in the first paragraph is insufficient, as compared

Example 1, the falling ball impact strength and surface gloss are not good; and when the amount of C.A.latex added in the first section is too much, such as Comparative Examples 2 and 3, the tensile strength becomes poor; if the first section and the second section add The time interval is not enough, as in Comparative Example 4, the high-temperature processability deteriorates, and a high-gloss resin cannot be obtained. However, adding C.A.latex in the existing one-step method, such as Comparative Examples 5 and 6, when high falling ball impact strength is desired, the tensile strength is deteriorated, and the gloss is also reduced. If C.A.latex is added in the existing continuous way, such as Comparative Examples 7 and 8, to obtain high falling ball impact strength, it will lead to poor formability during high temperature processing, and greatly reduce the gloss of molded products.

Claims (6)

1. the manufacture method through gatheringization rubber modified styrene series resin comprises: (1) is that the rubber latex of 0.04～0.18 μ m is added polymer coagulant (C.A.latex) gatheringizations contain the carboxylic acid group with median size, and making the formation median size is the gathering rubber latex of 0.23～1.0 μ m; (2) rubber latex after the gatheringization is in the presence of 100 weight parts (dry weight), can be monomer from aromatic vinyl, unsaturated nitrile is a monomer, select two or more monomer 10～150 weight parts in the methacrylate ester monomer, and can carry out graft polymerization with the monomer that contains unsaturated group 0～50 weight part of aforementioned monomer copolymerization, it is characterized in that: the C.A.latex addition manner that contains the carboxylic acid group in described (1) is the mode that is divided into more than two sections or two sections, and in the presence of the rubber latex of 100 weight parts (dry weight), first section addition of C.A.latex is 0.2～0.8 weight part; First section later addition summation is 0.8～5.9 weight part.

2. according to the manufacture method of claim 1, it is characterized in that in the presence of the rubber latex of 100 weight parts (dry weight) that first section addition the best of C.A.latex is 0.3～0.6 weight part; First section later addition summation the best is 1～3 weight part.

3. according to the manufacturing processed of claim 1, it is characterized in that C.A.latex is 10～60 minutes first period timed interval with second section interpolation.

4. according to the manufacturing processed of claim 1, it is characterized in that C.A.latex is 20～40 minutes first section timed interval the best with second section interpolation.

5. according to the manufacturing processed of claim 1, it is characterized in that C.A.latex first section with first section after the ratio 1: 1～1: 20 of addition summation.

6. manufacturing processed according to claim 1 when it is characterized in that the C.A.latex addition manner is divided into more than two sections or two sections, is in 3 minutes during every section interpolation.