JPH0641274A - Photocrosslinked polyester resin molding - Google Patents

Abstract

PURPOSE:To obtain the molding markedly improved in abrasion resistance without detriment to mechanical strengths. CONSTITUTION:The molding is produced by molding a composition comprising a resin (A) based on a saturated polyester, 5-50 pts.wt., per 100 pts.wt. A, cationically polymerizable compound (B) based on an epoxy resin containing at least two oxirane rings in the molecule, 0.01-20 pts.wt., per 100 pts.wt. B, photopolymerization initiator (C) which releases a Lewis acid catalyst upon ultraviolet irradiation and 5-150 pts.wt., per 100 pts.wt. total of A, B and C, reinforcement and photocrosslinking the obtained molding by irradiating part of the surface of this molding with an ultraviolet radiation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin molded product reinforced with a reinforcing material, and by partially photocrosslinking the surface thereof, it can be effectively used as a molded product having excellent wear resistance. The present invention relates to a photocrosslinkable polyester resin molded product.

[0002]

2. Description of the Related Art Conventionally, saturated polyester has been widely used in various molded products such as molds by adding a reinforcing material in addition to its excellent mechanical properties.

However, in recent years, with the miniaturization, weight reduction, precision, and sophistication of lifestyles of electronic devices, there has been a demand for a molded product having higher strength and excellent wear resistance.

In order to satisfy such required performance,
Japanese Patent Application Laid-Open No. 3-179052 discloses a composition containing specific composite particles, and Japanese Patent Application Laid-Open No. 2-173157 contains particles obtained by fusing silicone fine particles to the surface of inert inorganic particles. The resulting composition has been proposed.

[0005]

However, the molded product according to the above technique has a problem in practical use because it lowers the mechanical strength of the saturated polyester resin and increases the cost.

[0006] It is an object of the present invention to provide a polyester resin molded product having dramatically improved abrasion resistance at a low cost without lowering the mechanical strength.

[0006]

In order to solve the above-mentioned problems, the present invention has been fundamentally reexamined, and as a result, the molded body of the molded body has been obtained without lowering its mechanical strength. It has been found that a molded product having the characteristic only in the portion where abrasion resistance is required can be obtained.

That is, according to the present invention, a resin (A) containing a saturated polyester as a main component has two oxirane rings in one molecule.
A cationic polymerizable compound (B) containing at least one epoxy resin as a main component, a photopolymerization initiator (C) of the cationic polymerizable compound that liberates a Lewis acid catalyst upon irradiation with ultraviolet rays, and a reinforcing material (D), (B) is 5 to 50 parts by weight with respect to (A) 100 parts by weight, (C) is 0.01 to 20 parts by weight with respect to (B) 100 parts by weight, (D) is (A),
5 to 15 per 100 parts by weight of the total of (B) and (C)
A photo-crosslinked polyester resin molded article, characterized in that a composition blended at a ratio of 0 parts by weight is formed into a molded article, and a part of the surface of the molded article is irradiated with ultraviolet rays to be photocrosslinked.

The present invention will be described in detail below.

<Constituent Components> (1) Resin (A) Containing Saturated Polyester as Main Component The saturated polyester as the main component of the component (A) in the present invention is an aromatic component such as terephthalic acid or naphthalene dicarboxylic acid. Dicarboxylic acid or its ester-forming derivative is mainly used, and ethylene glycol, alkylene glycol such as tetramethylene glycol, cyclohexanedimethanol or its ester-forming derivative is mainly used as a glycol component, and a condensation-polymerized polymer is used. To be

Representative examples of those saturated polyesters include polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate or mixtures thereof.

In this case, as the acid component or the glycol component, 30 mol% or less of each other dicarboxylic acid, glycol or an ester-forming derivative thereof may be contained as a copolymerization component. Examples of such other type of copolymerization component include, as an acid component, an aliphatic dicarboxylic acid such as succinic acid, adipic acid, and sebacic acid, an alicyclic dicarboxylic acid such as tetrahydroterephthalic acid, and an oxy compound such as hydroxyethoxybenzoic acid. Carboxylic acid, etc.
Further, examples of the glycol component include polyalkylene glycols such as polyethylene glycol and polypropylene glycol.

The saturated polyester used in the present invention has an intrinsic viscosity of 0.4 to 1 when measured at 23 ° C. using a mixed solvent of phenol and tetrachloroethane in a weight ratio of 1: 1.
It is in the range of 2 dl / g, preferably 0.5 to 1.1 dl / g.
If it is less than 0.4 dl / g, the effect of the present invention is hard to be exhibited.
It is difficult to prepare the composition of the present invention when it exceeds 2 dl / g.

The resin (A) containing a saturated polyester as a main component of the present invention may be selected from other thermoplastic resins such as polycarbonate, polyamide, polyarylate, polyoxymethylene, as long as the characteristics of the saturated polyester are not lost. In addition to polyphenylene oxide, polyphenylene sulfide, polyethylene, polypropylene, ethylene-propylene copolymer, polystyrene, styrene-butadiene copolymer, and one or more kinds of saturated polyester oligomers may be blended.

(2) Cationic Polymerizable Compound (B) The cationic polymerizable compound used in the present invention is one of cationic polymerizable compounds containing an epoxy resin having two or more oxirane rings in one molecule as a main component, or It is a mixture of two or more kinds, and as such an epoxy resin, a bisphenol type epoxy resin, a novolac type epoxy resin, an alicyclic epoxy resin and the like are preferable.

As the bisphenol type epoxy resin,
For example, Epicoat 828, Epicoat 834, Epicoat 836, Epicoat 1001, Epicoat 1004,
Epicoat 1007 (above, Yuka Shell Epoxy Co.,
(Trade name), DER331, DER332, DER66
1, DER664, DER667 (above, Dow Chemical Co., trade name), Araldite 260, Araldite 2
80, Araldite 6071, Araldite 6084,
Araldite 6097 (above, product name by Ciba Geigy, Inc.) and the like can be mentioned, and these can be used alone or in combination.

As the novolac type epoxy resin,
For example, Epicoat 152, Epicoat 154 (all manufactured by Yuka Shell Epoxy Co., Ltd., trade name), Araldite EPN
1138, Araldite EPN1139, Araldite ECN1235, Araldite ECN1273, Araldite ECN1280, Araldite ECN1299
(Above, product name by Ciba-Geigy), DEN431,
DEN438 (above, product name of Dow Chemical Co., Ltd.) and the like can be mentioned, and these can be used alone or in combination.

As the alicyclic epoxy resin, for example, Epicoat 190P, Epicoat 191P (above, trade name of Yuka Shell Epoxy Co., Ltd.), Araldite CY175,
Araldite CY177, Araldite CY179, Araldite CY184, Araldite CY192 (above, Ciba Geigy, trade name), ERL-4221,
ERL-4299, ERL-4234 (above, Union Carbide company make, a brand name), etc. are mentioned, These are used individually or in mixture.

It is also possible to use a butadiene-based epoxy resin or the like, and a mixture of the above various epoxy resins can also be used.

As the cationically polymerizable compound (B) used in the present invention, a monofunctional epoxy diluent may be used as long as the curing property is not deteriorated. Examples of such a monofunctional epoxy diluent include butyl glycidyl ether, phenyl glycidyl ether, and t-butyl glycidyl ether.

It is also possible to use a cationically polymerizable vinyl compound mixed with the above-mentioned epoxy resin. Examples of such cationically polymerizable vinyl compound include styrene, allylbenzene, triallyl isocyanate and triallyl cyanate. , Vinyl ether, N-vinylcarbazole, N-vinylpyrrolidone and the like.

(3) Photopolymerization Initiator (C) Examples of the above-mentioned cationically polymerizable compound photopolymerization initiator which is incorporated into the composition of the present invention and liberates a Lewis acid catalyst upon irradiation with ultraviolet rays include aromatic diazonium salts. Examples thereof include aromatic halonium salts and photosensitive aromatic onium salts of Group VIb or Vb elements.

The aromatic diazonium salt is represented by the general formula (I)

[0023]

[Chemical 1]

[Wherein R ¹ and R ² are each a hydrogen atom, an alkyl group or an alkoxy group, R ³ is a hydrogen atom, an aromatic group or an aromatic group connected by an amide group or a sulfur atom, M
Represents a metal atom or a metalloid atom, and Q represents a halogen atom.
a is an integer of 1 to 6 and a = (bc) is satisfied, c is an integer of 2 to 7 and is equal to the valence of M, and b represents an integer of 8 or less larger than c].

A compound represented by

[0026]

[Chemical 2]

And the like.

The aromatic halonium salt has the general formula (II)

[(R ⁴ ) _d (R ⁵ ) _e X] _f ⁺ [MQ _g ] ^-(gh) (II)

[In the formula, R ⁴ is a monovalent aromatic group and R ⁵ is 2
Valent aromatic group, X is a halogen atom, M is a metal atom or a metalloid atom, Q is a halogen atom, d is 0 or 2, e
Is 0 or 1 and (d + e) is equal to the valence of 2 or X, g is an integer greater than or equal to 8 and less than or equal to f,
= G−h]

A compound represented by

[0032]

[Chemical 3]

And the like.

Further, the group VIb element or the photosensitive aromatic onium salt of the group Vb element is represented by the general formula

[(R ⁶ ) _i (R ⁷ ) _j (R ⁸ ) _k Y] _r ⁺ [MQ _m ] ^-(mn) (III)

(Wherein R ⁶ is a monovalent aromatic group, R ⁷ is a monovalent aliphatic group selected from the group consisting of an alkyl group, a cycloalkyl group and a substituted alkyl group, and R ⁸ is an aliphatic group. And a polyvalent group constituting a heterocyclic structure selected from an aromatic group, Y is an element of Group VIb of S, Se, Te or N, P, As, Sb
And a group Vb element selected from Bi, M represents a metal element or a metalloid element, and Q represents a halogen atom. i is an integer of 0 to 4, j is an integer of 0 to 2, k is an integer of 0 to 2, and (i + j + k) is equal to the valence of Y, and Y is VIb.
Equals 3 for a clan and 4 for Y of the Vb group, r =
(M−n) is satisfied, and n is an integer of 2 to 7 and is equal to the valence of M, and m represents an integer of 8 or less and larger than n).

Is a compound represented by:

Examples of onium salts of Group VIb elements include, for example:

[0039]

[Chemical 4]

And the like.

Examples of onium salts of Vb group elements include

[0042]

[Chemical 5]

And the like.

(4) Reinforcing Material (D) The reinforcing material in the present invention is a fibrous or granular inorganic and / or
Or it is an organic substance. Examples of the fibrous reinforcing material include glass fiber, shirasu glass fiber, alumina fiber, silicon carbide fiber, ceramics fiber, asbestos fiber, gypsum fiber, stainless fiber, carbon fiber, and Kevlar fiber (trade name, manufactured by DuPont, USA). To be Further, as the granular reinforcing material, silicates such as wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc and alumina silicate; metal oxides such as alumina, zirconium oxide and titanium oxide; calcium carbonate, Carbonates such as magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate, glass beads, glass flakes, boron nitride, silicon carbide,
Examples include Saloyan. These reinforcing materials may be used alone or in combination of two or more. If necessary, the above reinforcing material may be pretreated with a silane-based or titanium-based coupling agent before use.

(5) Blending ratio The blending amount of the cationically polymerizable compound (B) with respect to the resin (A) whose main component is saturated polyester is 10
5 to 50 parts by weight, preferably 10 to 4 parts by weight
5 parts by weight, more preferably 15-40 parts by weight.

If the added amount of the component (B) exceeds 50 parts by weight, the obtained molded product has poor flexibility, and if it is less than 5 parts by weight, the heat resistance is poor.

The amount of the photopolymerization initiator (C) added to the cationically polymerizable compound (B) is 0.01 to 20 parts by weight, preferably 100 parts by weight of the cationically polymerizable compound (B). It is 1 to 15 parts by weight, and if it is less than 0.1 parts by weight, the crosslinking reaction rate by ultraviolet rays tends to be slow and the treatment time tends to be too long. If the amount exceeds 20 parts by weight, the cost of the catalyst is high, so that not only the price of the resin composition increases, but also the strength of the molded body decreases and the characteristics of the molded body deteriorate significantly due to a large amount of residual ionic components.

The amount of the reinforcing material (D) added to the total amount of the components (A), (B) and (C) is (A),
5 to 15 per 100 parts by weight of the total of (B) and (C)
When the amount is 0 parts by weight and the amount is less than 5 parts by weight, the strength of the molded product is remarkably reduced, and when it exceeds 150 parts by weight, the crosslinking reaction is delayed and the strength of the molded product is remarkably reduced.

<Manufacture of Molded Article> The photo-crosslinked polyester resin molded article of the present invention can be formed into various molded articles by a known injection molding method after melt-mixing the above components before photo-crosslinking. .

(1) Melt Mixing In order to produce the photocrosslinked polyester resin molded product in the present invention, usually, a resin (A) containing saturated polyester as a main component and a cationically polymerizable compound (B) are first formed into a ribbon. The mixture is mixed by a mechanical mixing means such as a blender or a V-type blender, and further melt-kneaded using a melt-kneader such as an extruder to obtain pellets. The melt-kneading is generally carried out at a temperature not lower than the melting temperature of the polyester resin for 1 to 10 minutes. The photopolymerization initiator (C) is usually preferably added and kneaded in the next molding step in order to avoid decomposition of the photopolymerization initiator.

(2) Molding processing The obtained pellets are dry-blended with the photopolymerization initiator (C) and then molded by various ordinary injection molding machines for thermoplastic resins.

<Ultraviolet Irradiation> It is preferable that the irradiation of ultraviolet rays is continuously carried out only on a required partial surface of the molded body following the molding step, but it is carried out in another step after the molded body is obtained. It can also be implemented. UV irradiation conditions are
The irradiation time is 100 seconds or less, preferably 60 seconds or less and 1 second or more at a temperature of room temperature or higher and the melting point of the polyester resin or lower. If the irradiation time exceeds 100 seconds, the polyester resin is likely to deteriorate, which is not preferable. In addition, it also requires a large amount of equipment, which reduces the line speed in the molding process.

Ultraviolet rays having a wavelength of 100 to 500 nm, preferably 200 to 450 nm are generally used.

[0054]

EXAMPLES The method for producing the photo-crosslinked polyester resin molding of the present invention will be specifically described below.

Examples 1 and 2 Polybutylene terephthalate (A) (melting point 221 ° C.) obtained by using terephthalic acid as an acid component and butylene glycol as a glycol component, and bisphenol A
Type epoxy resin (B) (Okaka Shell Epoxy Co., Epicoat 828) and glass fiber (D) (Nippon Electric Glass Co., T198H) were mixed in the proportions shown in Table 1 and mixed well with a V-type blender. , L / D = 30, 30 mm diameter twin-screw kneader (PCM type made by Ikegai Tekko Co., Ltd.) with a cylinder temperature of 2
Melt kneading was performed at 40 ° C. and a screw rotation speed of 200 rpm to obtain pellets as a molding material.

Then, as a photopolymerization initiator, 4,4'-bis [di- (β-hydroxyethoxy) phenylsulfonyl] phenyl sulfide-dihexafluoroantimonate (C) was previously melt-pelletized into a molding material [ (A)
+ (B)], the amounts shown in Table 1 are added and mixed in a V-type blender, and a 100-ton injection molding machine (J-100 type manufactured by Japan Steel Works, cylinder temperature 240 ° C., mold temperature) is used. 8
A sheet having a thickness of 2 mm was formed by using (0 ° C.).

A high pressure mercury lamp (80w /
(cm) was irradiated for 10 seconds at 80 ° C. from a position separated by 10 cm.

Table 1 shows the results of the abrasion test and the bending strength test of the obtained sheet.

The test method is as follows.

(1) Evaluation of abrasion resistance The obtained sheet molding was cut into a square of 30 mm and a thickness of 2 mm.
Under the load of 2.8 kg / cm ² , the sheet test piece of No. 1 was brought into contact with the end surface of the hollow counterpart material made of iron, and a sliding wear test was conducted. At this time, the temperature of the test piece was simultaneously adjusted so that the test piece temperature was in the range of 25 to 35 ° C. The wear test was stopped when the sliding distance reached 1.5 km, and the change in weight before and after the test was taken as the wear amount. As the tester, ITA-40 / 3000-04A type manufactured by Tokyo Tester Manufacturing Co., Ltd. was used.

(2) Bending strength test ISO R178-1974 Procedure 12 (JIS
K7203) and measured using an Instron tester.

[0062]

[Table 1]

Comparative Examples 1 to 4 Comparative Examples 1 to 4 were carried out in the same manner as in Examples 1 and 2 except that the conditions of UV irradiation and the compounding amounts were in accordance with the conditions shown in Table 1. The results are shown in Table 1.

The sheets obtained in the respective examples in Table 1 had better wear resistance and better mechanical strength than the sheets of the comparative examples. That is, the effect of photocrosslinking the surface of the molded body is clear.

[0065]

EFFECT OF THE INVENTION The photocrosslinking polyester resin composition of the present invention is capable of dramatically increasing abrasion resistance, preventing mechanical strength from being lowered, and having a high strength sliding material. Is effectively used as.

Claims (1)

[Claims] 1. A resin (A) containing a saturated polyester as a main component, a cationically polymerizable compound (B) containing an epoxy resin having two or more oxysilane rings in a molecule as a main component, and a Lewis acid catalyst by ultraviolet irradiation. It consists of the photopolymerization initiator (C) and the reinforcing material (D) of the cationically polymerizable compound which is liberated, and (B) is 5 to 50 parts by weight with respect to 100 parts by weight of (A), and (C) is (B). ) A composition in which 0.01 to 20 parts by weight per 100 parts by weight and (D) are blended in a ratio of 5 to 150 parts by weight based on 100 parts by weight of the total of (A), (B) and (C). A photo-crosslinked polyester-based resin molded article, characterized in that the article is formed into a molded article, and a part of the surface of the molded article is irradiated with ultraviolet rays to be photocrosslinked.