JPH02150462A - Surface-treating agent - Google Patents

Abstract

PURPOSE:To obtain a surface-treating agent having affinity and adhesivity to filler and substrate by reacting an organic titanate with a polymer containing a plurality of specific groups such as carboxyl group in the molecule and using the obtained Ti-containing polymer as a component. CONSTITUTION:The objective surface-treating agent contains a Ti-containing polymer produced by reacting an organic titanate [expressed by (R1O)3TiX] with a polymer containing two or more of at least one kind of groups selected from carboxyl group, carboxylic acid anhydride group and hydroxyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a surface treatment agent such as a filler used in combination with a polymer, and more particularly to a surface treatment agent containing a Ti-containing polymer.

[Conventional technology]

Polymer-based molded products are generally composited with fillers to improve dimensional stability and heat resistance, but on the other hand, composites may reduce processability or mechanical properties. It's inviting.

A method of adding a titanium compound is known as a means of solving the problems of composites using polymeric fillers.
As described in Vol., March issue, No. 26i (t982), it is said to be effective even for fillers such as calcium carbonate or calcium sulfate, which are ineffective with silane coupling agents.

However, its performance is not necessarily effective in improving reinforcing properties, such as adhesion promotion performance.・Such conventional silane- or titanium-based coupling agents have a comparatively large number of carbon atoms in the organic group bonded to the silane or titanium via oxygen. The target is small (
(for example, 18 or less).

On the other hand, reinforcement of rubber using calcium carbonate or silicate treated with polybutadiene having a carboxyl group or a carboxylic acid anhydride group is described in JP-A-53-147743 and JP-A-55-13791. However, when treated with polybutadiene compounds, the Journal of Applied Polymer Science found that polybutadiene groups alone lack the ability to form water-resistant bonds with fillers and substrates.
rnal or Applied Polymer 5
science) Vol, 29 (1984) 3rd t.
s2g.

In addition, the use of calcium carbonate treated with a specific polycarboxylic acid to improve the dispersibility and surface gloss of a water-based paint is disclosed in JP-A-62-212479 and JP-A-62-212480. It is stated in

[Problem to be solved by the invention]

In the above-mentioned prior art, when a filler is mixed with a polymer, (1) well-known polybutadiene carboxylic acid etc. are effective, but according to the study of the present inventors, these The adhesion force is insufficient, and for example, when a molded product composited with a filler is immersed in water, the physical properties deteriorate significantly.

(2) Certain polycarboxylic acids are ineffective or have little effect on some type Il fillers.

There were various drawbacks such as.

Therefore, an object of the present invention is to provide a surface treatment agent that improves the problems of these prior art techniques.

[Means to solve the problem]

The surface treatment agent of the present invention is produced by reacting an organic titanate with a polymer containing in its molecule two or more groups of at least one type selected from the group consisting of a carboxyl group, a carboxylic acid anhydride group, and a hydroxyl group. It contains the obtained Ti-containing polymer.

The present invention will be explained in detail below.

(]) Raw material polymer The polymer has two or more groups of at least one type selected from the group consisting of carboxyl group, carboxylic acid anhydride group, and hydroxyl group in the molecule, and has a molecular weight of 5.
00 to 5,000 homopolymer or copolymer. In the case of a copolymer, it may be either a random copolymer or a block copolymer, and if the molecular weight is less than 500, the improvement in physical properties, which is the objective of the present invention, will not be observed; If it is larger than ooo, the surface treatment agent itself becomes too large and becomes difficult to adhere effectively to the filler surface.

The method for producing the above polymer is as follows.

Polymerize a monomer having an unsaturated double bond and having at least one group selected from the group consisting of a carboxyl group, a carboxylic acid anhydride group, and a hydroxyl group, or having an unsaturated double bond. Add nanatsumer and polymerize.

Examples of monomers used here are as follows.

At least III monomers such as ethylene, propylene, butylene, butadiene, isoprene, styrene, α-methylstyrene, (meth)acrylic ester, vinyl acetate, acrylonitrile, vinyl ester, vinyl ether, etc.

At least L of vinyl [2, (anhydrous) maleic acid, fumaric acid, (meth)acrylic acid, crotonic acid, (anhydrous) itaconic acid, vinyl alcohol, P-vinylphenol, etc. (2) Organic titanates mentioned above used in the present invention The am titanate reacted with a polymer having a carboxyl group, an acid anhydride group, or a hydroxyl group is a compound represented by -Funazo (RI 0) 3TiX.

R5 in the above formula represents the same or different hydrocarbon groups having 1 to 8 carbon atoms or these groups having substituents, and the hydrocarbon groups are alkyl groups and alkenyl groups, and specific examples of these groups include: CHz -CgHs, (CHi)xCH-1nC
aH*CJ! CHx Cut NH
zCHtCHx, etc.

Moreover, X in the above formula is the general formula R10-1R, COO-1R1503-(RlC)!
represents a group selected from the group consisting of PG- and , specifically, CHsC*Hs −~C+tHxsCiHa, C
tJsy-, etc., and Y is a methyl group or an alkoxy group having 1 to 4 carbon atoms, specifically, C11sO-1CjH,0-1CaH*O-.

(3) Ti-containing polymer The Ti-containing polymer can be easily obtained by reacting the raw material polymer and the organic titanate at 10 to 100°C for about 30 minutes to 5 hours, usually in the presence of a solvent. can.

As the solvent, a solvent that dissolves the polymer and organic titanate compound, such as toluene, hexane, and ethyl acetate, is used, and the amount used is about 50 to 500 parts per 100 parts of the polymer.
Department.

When an organic titanate is added to a polymer having a carboxyl group, a carboxylic acid anhydride group, or a hydroxyl group during the synthesis of the Ti-containing polymer of the present invention, gelation may occur due to intermolecular crosslinking. To prevent this, a chelating agent can be added to the organic titanate in advance.

Examples of the chelating agent include β-diketones such as acetylacetone and benzoylacetone, α- or β-ketonic acid groups such as acetoacetic acid and propionylbutyric acid, and lower alkyls of these ketonic acids such as methyl, ethyl, propyl, and butyl. Esters can be mentioned.

The obtained Ti-containing polymer has the following partial structure.

(4) Preparation of surface treatment agent The above Ti-containing polymer is used as it is or dissolved in a solvent.

The solvent for dissolving the surface treatment agent may be any solvent as long as it dissolves the surface treatment agent well, but the following are generally used.

These include benzene, toluene, xylene, hexane, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, dioctyl adipate, and the like.

Further, other surface treatment agents may be used in combination.

(5) Surface treatment of fillers, etc. Examples of methods for treating fillers, etc. using the surface treatment agent of the present invention include the following methods.

1) A method of adhering the filler to the filler by dropping or spraying the surface treatment agent composition or its solution while stirring the filler, and then drying it. ii) A method in which the filler or the substrate is placed in the solution of the surface treatment agent composition. Method of drying after immersion iii) Method of mixing the filler and surface treatment agent composition in a resin medium iv) Adding the surface treatment agent composition in advance to a resin medium having no reactive functional groups, such as a plasticizer, etc. A method is used in which a filler is mixed after the mixture is allowed to stand, and the method of use thereof is not particularly limited.

The amount of these surface treatment agents used is 0.1 to 5 parts by weight, preferably 0.5 to 2.0 parts by weight, per 100 parts by weight of the filler.
5 parts by weight. 0.1! If the amount is less than 1 part by weight, the effect is small, and even if 5 parts by weight or more is added, the expected increase in effect is not observed, but this is not intended to limit the scope of the present invention.

Fillers that can be treated with the above-mentioned surface treatment agent include those described in Kozo Sato, "Physical Properties of Filled Polymers", pp. 8 and 9, Riko Shuppansha (197B). "A relatively inert solid substance added to polymeric materials for the purpose of reducing unit cost, improving processability and physical properties, imparting color effects, etc." As shown in the page, it contains "pigments and extender pigments known in the paint industry", and these fillers include, for example, calcium carbonate, kaolin, clay, mica, talc, wollastonite, calcium silicate, and titanium oxide. , iron oxide, calcium sulfate, barium sulfate, silica, carbon black, glass fiber, and other inorganic compounds; aluminum,
These include metal powders such as nickel and zinc.

In addition, the substrate to be surface treated is a tangible object such as a gold plate or a ceramic plate.

Further, as a result of studies by the present inventors, examples of polymers on which the surface treatment agent of the present invention effectively acts include polyethylene, polypropylene, EVA, and EEA.

Polyolefin resins such as PVC; polymers with unsaturated bonds such as ABS and rubbers (polybutadiene, SBR, NR, EPDM); diallyl phthalate resins, (meth)acrylic resins, polyester resins, polysulfone resins, polyamide resins and maleimides resins, etc., but these do not limit the embodiments of the present invention.

It can be used in a wide range of applications such as molded products, painting, and forming adhesive layers.

〔Example〕

(Production of raw material polymer (a) Sample A-1 (polymaleic anhydride) 11,300 g of maleic anhydride, 200 g of monochlorobenzene, and 100 g of xylene were placed in a reaction vessel and heated to reflux at 140°C.

100 g of di-tert-butyl peroxide, 100 g of monochlorobenzene, and 50 g of xylene were mixed at room temperature and added to the refluxing solution of maleic anhydride over 4 hours.

Reflux is complete when the addition is continued for an additional 4 hours.

The reaction was now cooled to 100° C. to allow the polymer to precipitate. The lower layer of anhydrous polymer (approximately 328 g) was poured into 300 g of water with stirring.

In order to completely hydrolyze the above reactant, at 100℃
The mixture was heated to reflux for 0 minutes and then cooled to 60-70°C. Approximately 60 g of monochlorobenzene/xylene mixture was added to 6
Distillation was carried out at a temperature of 0 to 70°C and a pressure of 2Q tea HH over a period of about 30 minutes.

The product was filtered to make it finally clear.

Product (A-1) is yellow in color and is an amber liquid cane whose solids content is 50% W/W.

The number average molecular weight of the product was 1060.

c) Sample A-2 (monoisopropyl maleate-styrene copolymer) Negoo with Banbury type rotor blade (inner volume 127!
, f! Using a stirring motor (2 HP) as a reactor, 10 moles of maleic acid monoisopropyl ester (158
0 g) and 12 moles (124 Bg) of styrene were weighed out, mixed together, and heated to 90"C, and then 0.3 moles (72 °6 g) of benzoyl peroxide, a polymerization catalyst, was added over 30 minutes. At the same time as the reaction started, the reaction temperature was raised to 130°C in 10 minutes after adding the polymerization catalyst due to the heat of polymerization.
The reaction was continued at this temperature. After the start of the reaction, the first 30
It was a low viscosity liquid for a few minutes, but the viscosity gradually increased,
The resulting copolymer had a high viscosity and was kneaded by a rotary blade, and as the polymerization reaction progressed, the copolymer gradually grew and thickened. After reacting for 3 hours, the reaction product was cooled, the temperature was lowered to about 90°C, and the polymer was kneaded and cut, and then pulverized at about 80 to 85°C to form a powder. In this way, a light yellow powdered polymer (
A-2) 2800g was obtained. Furthermore, as a result of analyzing and quantifying the unreacted monomer of this copolymer by gas chromatography,
The content of styrene was 0.5% (weight), and the content of maleic acid monoester was 1.5% (weight).
Its intrinsic viscosity (η) in dioxane solvent is −0.42, and its softening point is 125-135°C.

The number average molecular weight of the product was 1200, and the composition of the copolymer determined by elemental analysis was 45 mo1% monoisopropyl maleate and 55 mo1% styrene.

(C) E material A-3 (styrene-acrylonitrile-
Maleic anhydride copolymer) 1 with reflux condenser, stirrer and drip coat
150 g of maleic anhydride in a flask.

120 g of acrylonitrile and 36 g of t-dotesylmercaptan were charged, heated to 75° C., and while stirring thoroughly, styrene was continuously added dropwise at a rate of 30 g/hour. Polymerization progressed as styrene was added dropwise, and the polymerization solution gradually became a viscous liquid.

The dropping of styrene was stopped 4 hours after the start of dropping (styrene dropping amount: 126 g), and the produced copolymer (A-3) was collected. The amount of copolymer produced was 251g (polymerization rate 64.4%)
), the number average molecular weight of the product is 1200, the composition of the copolymer determined by elemental analysis is 32 mol % styrene,
Acrylonitrile 47 mol%, anhydrous maleic #20
sol %, heat distortion temperature (BS method HD T ) is 161
“It was C.

When the styrene dropwise addition was completed, a portion of the polymerization solution was sampled and a quantitative analysis of the remaining styrene monomer was performed by gas chromatography, but almost no amount could be detected.

(d) Sample A-4 (ethyl vinyl ether-maleic anhydride copolymer) 1, 1. 2-) ri ri ro ro −
1,2,2-trifluoroethane 50.51 ift% and dichloromethane 4
9.5% by weight azeotrope 150d, anhydrous maleic II
6.65 g of I and 5.40 g of ethyl vinyl ether
300g equipped with a cooler, stirrer and temperature meter
iPut it into the flask. After keeping the mixed solvent at the reflux temperature (36.5° C.) for 10 minutes while stirring, 0.2 g of t-butyl peroxypivalate was added and polymerization was carried out for 4 hours.

When the stirring was stopped, the produced copolymer could be easily taken out in a suspended state without adhering to the flask wall or the stirring blade, and was filtered through a filter paper. After drying, the yield is 1
It was 0.14 g (-next removal).

In addition, the copolymer (A-4) that had not become suspended but had precipitated at the bottom of the flask was taken out and dried.

The yield was 2.27 g (secondary extraction).

8i! of the obtained copolymer! The limiting viscosity (η) is 1.330 (
Methyl ethyl ketone, 35°C).

The number average molecular weight of the product is 15oO, and the composition of the copolymer determined by elemental analysis is ethyl vinyl ether 4
8 mol % and maleic anhydride 52 s+ol %.

(e) EI4A-5 (styrene-maleic anhydride copolymer) 7°2 in a Pyrex polymerization tube with an internal volume of 100 ml
XlO-” moles (7,49 g) of styrene, 7,2×
An acetone solution containing 10-" moles (7,06 g) of maleic anhydride and 5°7 x 10-" moles (6,89 g) of dimethylaniline was taken, and α as a polymerization initiator was taken.
・α-Azobisisobutyronitrile was added at 5XlO mol/l, degassed under vacuum, and replaced with nitrogen, then sealed, placed in a shaking polymerization tank, and polymerized for 1 hour while maintaining the temperature at 60°C. After the completion of the reaction, the polymerization tube was opened and the reaction mixture was concentrated and mixed with chloroform-petroleum ether (1:2
) The cooligomer precipitated by treatment with the mixed solution was fractionated, purified and dried, and used as a sample. The product (A-5) had a yield of 13%, a number average molecular weight of 1876, and the composition of the copolymer determined by elemental analysis was styrene 4B, 5*ol %, maleic anhydride 51.5*ol %.

(f) Sample A-6 (polyacrylic acid) written by Eizo Omori “
"Functional Acrylic Resin" (Published by KK Techno System 1)
Polyacrylic acid was synthesized by the method described on page 27 (1985).

The average molecular weight is 1,000, and the AV nearness is 1.9.

(2) Sample A-7 (acrylic acid-methyl acrylate polymer) An acrylic acid-methyl acrylate copolymer was synthesized by the method described on page 36 of "Functional Acrylic Resin" above.

Average molecular weight is 1,400, AV': 479? The composition of the copolymer was 15 sol % acrylic acid content and 85 mol % methyl acrylate content.

(h) Sample A-8 (fully saponified polyvinyl alcohol) -02 to Denka Poval manufactured by Denki Kagaku, 98.5 degree of fight
%, average degree of polymerization 250 (i) Sample A-9 (poly P-vinylphenol)
Maruzen Petrochemical Resin M, average molecular M3.000, OH
V: 120 (2) Synthesis of Ti-containing polymer U) 1060 g of polymaleic anhydride (A-1) synthesized in (1) (a) was added to 1060 g of Improper Tool.
dissolved in. 6134g of tetrabutoxytitanium (
21.6 mol) and 2160 g of acetylacetone. Thereafter, the mixture was heated and stirred at 80° C. for 2 hours.

The solvent was heated to 40°C and 20 wtm Hg? Removal was carried out under reduced pressure to obtain a reaction product (T-1).

As a result of IR absorption spectrum analysis, this (T-1) showed that the absorption based on the acid anhydride group of the raw material polymaleic anhydride had disappeared, and it had absorption based on acyloxytitanium. Further, the result of TR spectrum analysis (T-1) showed absorption of carbonyl group coordinated to Ti.

(B) By the same reaction as A-1, (A-2) to (A
-9), a titanium alkoxide derivative was also synthesized. Table 2 shows the cultivated titanate and its amount to be reacted with the polymer having carboxyl group, acid anhydride group or hydroxyl group.

(3) Evaluation test (a) Polyether polyol talc system (2) (j)
Surface treatment agents (T-1) to (T-9) containing the Ti-containing compound synthesized in (g) and their raw materials (A-1) to (A
-9) was used to carry out the next trial %41.

Using a Henschel mixer, 100 parts of talc (manufactured by Shiraishi Kogyo Co., Ltd.) was treated with each surface treatment agent of the present invention in the amounts shown in Table 3, and then 80 parts of these treated products and Di
100 parts of al'-3000 (manufactured by Mitsui Nisso Urethane Co., Ltd., polyether polyol) were thoroughly mixed, and the viscosity of this mixture at 25°C was measured.

These results are shown in Table 3.

*l: Number of parts blended in terms of solid content per 100 parts of filler talc (C) Polypropylene-calcium carbonate system (2) Surface treatment agent containing a Ti-containing polymer synthesized from
-2), (T-5) and (T-7) were used to conduct the following test.

Using a Henschel mixer, 100 parts of calcium carbonate (Whiten 5SB, manufactured by Shiroishi Kogyo KK) was treated with the amount of each surface treatment agent of the present invention shown in Table 4, and then 60 parts of these treated products and polypropylene ( Manufactured by Ube Industries, J-
605H) were kneaded with two rolls heated at 185 to 190°C, cooled, and then pulverized.

The melt viscosity of these pulverized products was measured using a melt indexer. In addition, these pulverized products were heat pressed (200℃,
500kg/cj) for 7 minutes, tensile strength,
The elongation at break and the Izot impact value were measured. In addition, the tensile strength and Izodt street impact strength were also measured after the test pieces were immersed in water at 50° C. for 4 days.

In addition, as reference comparison samples, a system without surface treatment agent, raw materials (A-2), (A-5), and polybutadiene dicarboxylic acid (molecule N4,0) were similarly tested.

These results are shown in Table 4.

(c) Using surface treatment agents (T-2), (T-3) and (T-5) containing the Ti-containing polymer synthesized in (b) of PVC-calcium carbonate system (2). The following test was conducted.

Using a Henschel mixer, 40 parts of calcium carbonate (Whiten 5S, manufactured by Shiraishi Calcium Co., Ltd.) was added to the above (T-2),
(T-3) and (T-5) were treated in the amounts shown in Table 5, and then the treated product was added to 60 parts of PVC resin (Mitsubishi Monsando Vinica 37M1 polymerization degree 800) and 40 parts of dioctyl phthalate. The mixture was kneaded for 15 minutes using two rolls heated to 120 to 130°C.

The melt viscosity of these kneaded products was measured using a melt indexer. In addition, these kneaded materials were heat-pressed (200℃
, 40 to 50 kg/cm) for 5 minutes, and the tensile strength, elongation, and hardness were measured. The tensile strength was also measured after the test piece was immersed in water at 50°C for 4 days.

Further, as reference comparison samples, the same tests were conducted using raw materials (A-2) and (A-3) containing no surface treatment agent and polybutadiene dicarboxylic acid (described above).

These results are shown in Table 5.

(d) Polyethylene phthalate resin-glass short fiber system Surface treatment agent (T-1), (T-6), (T-8) containing the Ti-containing polymer synthesized in (2) 0) and (g)
) and (T-9) were used to conduct the following test.

Using a Henschel mixer, 30 parts of short glass fibers (chipped strand length 5m, diameter 9μ) were added to the above (T-1
), (T-6), (T-8) and (T-9) in the amounts shown in Table 6, and then the treated product was added to 70 parts of polyethylene phthalate resin (molecular weight 9000) and 2
The mixture was kneaded for 15 minutes using two rolls heated to 60°C, cooled, and then ground.

The melt viscosity of these pulverized products was measured using a melt indexer. In addition, these pulverized products were heat-pressed (260℃
, 500 kg/cd) for 5 minutes, and the tensile strength, bending strength, and elongation were measured. The tensile strength and bending strength were also measured after the test piece was immersed in water at 50°C for 4 days.

Further, as a reference comparative sample, a similar test was conducted using a system without surface treatment agent, raw materials (A-1), (A-6), and polybutadiene dicarboxylic acid (described above).

These results are shown in Table 6.

(e) Surface treatment agents (T-2), (T-4), (T-8) and (T-8) containing the Ti-containing polymer synthesized in (g) of polysulfone resin-silica system (2).
-9) was used to conduct the following test.

Using a Henschel mixer, 30 parts of silica (Crystallite CMC-1 manufactured by Ryumori Co., Ltd.) was added to the above (T-2) and (T-
4), (T-8), and (T-9) were treated in the usage amounts shown in Table 7, and then the treated product was added to 100 parts of polysulfone resin (P-1700 manufactured by Yasan Kagaku Co., Ltd.) to give 360 parts. The mixture was kneaded for 20 minutes using two rolls heated to 0.degree. C., and after cooling, it was pulverized.

The melt viscosity of these crushed materials was measured using a capillary rheometer (
(manufactured by Instron). In addition, these pulverized products were heated at a resin temperature of 360°C, an injection pressure of 2000 kg/d,
Injection molding is performed at a mold temperature of 150°C to determine tensile strength, elongation,
Bending strength and flexural modulus were measured. The tensile strength and bending strength were also measured after the test piece was immersed in water at 50°C for 4 days.

Further, as a reference comparative sample, a similar test was conducted using threads containing no surface treatment agent, raw materials (A-2) and (A-4), and polybutadiene dicarboxylic acid (described above).

These results are shown in Table 7.

(f) Surface treatment agents (T-1), (T-3), (T6) and (T -7)
The following test was conducted using

Using a Henschel mixer, 30 parts of wollastonite was mixed with the above (T-1), (T-3), (T-6) and (T-
7) in the amount shown in Table 8, then the treated product was added to 70 parts of nylon 6 (degree of polymerization 600) and heated at 250°C.
The mixture was kneaded for 20 minutes using two heated rolls, cooled, and then ground.

The melt viscosity of these pulverized products was measured using a melt indexer. In addition, these pulverized materials were heated to a resin temperature of 240°C.
Injection molding was performed at an injection pressure of 1200 kg/cd and a mold temperature of 80° C., and the tensile strength, bending strength, and bending elastic modulus were measured. The tensile strength and bending strength were also measured after the test piece was immersed in water at 50°C for 4 days.

Further, as a reference comparison sample, a system without a surface treatment agent, raw materials (A-1) and (A-3), and polybutadiene dicarboxylic acid (described above) were used for the same test.

These results are shown in Table 8.

(g) HDPE-talc-based (2) surface treatment agents (T-1), (T-2) and (T-2) containing the Ti-containing polymer synthesized in (jl and (k))
The following test was conducted using T-5).

Using a Henschel mixer, 25 parts of talc (Japan Talc, Simbon) were mixed with the above (T-1), (T-2) and (
T-3) was treated with the usage conditions shown in Table 9, and then the treated product was treated with HDPE (manufactured by Mitsui Petrochemical Co., Ltd., HIZEX 13).
00 J), kneaded for 20 minutes with two rolls heated to 150°C, cooled, and then crushed.

The melt viscosity of these pulverized products was measured using a melt indexer. In addition, these pulverized products were heat-pressed (180℃
, 500 kg/cd) for 5 minutes, and the tensile strength, flexural strength, and flexural modulus were measured. The tensile strength and bending strength were also measured after the test piece was immersed in water at 50°C for 4 days.

Further, as a reference comparison sample, a similar test was conducted using a system without a surface treatment agent, raw materials (A-1) and (A-2), and polybutadiene dicarboxylic acid (described above).

These results are shown in Table 9.

(h) Surface treatment agents (T-3), (T-6), (T-7) and (T-7) containing the Ti-containing polymer synthesized in (k) of methacrylic resin-mica system (2)
Using (T-8), the above (T-3), (
T-6), (T-7) and (T-8) were treated in the amounts shown in Table 1O, then the treated mica was added to 100 parts of methacrylic resin (average molecular fitlo, 000) and 25
The mixture was kneaded for 30 minutes using two rolls heated to 0°C, and then cooled and pulverized.

The melt index of these pulverized products was measured. In addition, these pulverized products were heat-pressed (230℃, 700kg/
cd) for 5 minutes, and the tensile strength and surface gloss were measured. The test piece was also measured after being immersed in water at 50°C for 4 days.

In addition, as reference comparison samples, a system without surface treatment agent and raw materials (A-3), (A-6), (A-7) and (A-8) were similarly tested.

These results are shown in Table 10.

(S) Surface treatment agents (T-3), (T-6), (T-7) and (
T-8), 100 parts of an acrylic resin solution (manufactured by Dainippon Ink & Chemicals KK, Acridic A-166),
The amounts shown in Table 11 were added to 50 parts of titanium oxide, mixed well to form a paint, and the viscosity of the paint was measured. Also, li
This paint was applied to I'4IXJ I5G-3141 and baked for 5 minutes to examine gloss, pencil hardness, adhesion and flexibility. The adhesion was also measured after the test piece was immersed in water at 50''C for 4 days.

Further, as reference comparison samples, similar tests were conducted using raw materials (A-3) and 1 (A-6) without the addition of a surface treatment agent.

These results are shown in Table 11.

〔Effect of the invention】

The surface treatment agent of the present invention has a plurality of alkoxy groups in one molecule that have affinity and adhesive properties with the filler and the substrate, and has a strong adhesion force to the filler surface.

In addition, the main chain of the surface treatment agent of the present invention is composed of a polymer with a large molecular weight (MW - 500 to 5000), and its affinity and compatibility with polymer media are significantly improved. It is effective in reducing melt viscosity, improving dispersibility, and improving mechanical properties, especially moisture resistance.

The surface treatment agent of the present invention is also characterized in that it can be applied to many types of fillers.

Applicant (430) Nippon Soda Co., Ltd.

Claims (1)

[Claims] (1) A Ti-containing polymer obtained by reacting an organic titanate with a polymer containing two or more groups in the molecule of at least one group selected from the group consisting of carboxyl groups, carboxylic acid anhydride groups, and hydroxyl groups. A surface treatment agent characterized by containing coalescence.