JPH0453812A - Molding composition and production of molded article therefrom - Google Patents

Abstract

PURPOSE:To improve the impact resistance of a molded article by mixing a molding compsn. comprising a thermoplastic resin, a (meth)acrylate, a fibrous component, and a polymn. initiator with a specified amt. of a polymerizable polar monomer. CONSTITUTION:A thermoplastic resin (e.g. a vinyl chloride resin), a mono- or polyfunctional (meth)acrylate (e.g. 2-ethylhexyl methacrylate), a fibrous component (e.g. a glass fiber), a polymn. initiator (e.g. t-butyl peroxybenzoate), and a polymerizable polar monomer (e. g. isophthalic acid monoacrylic ester) in an amt. of at least 0. 05 wt. % of the (meth)acrylate are mixed to give a molding compsn., which, when cured thermally or by exposing to a radiation, gives a molded article excellent in elastic modulus, bending strength, impact resistance, etc., and suitable for an electric part, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a molding composition and a method for producing a molded article.

[Prior Art] Compositions comprising vinyl chloride resins and (meth)acrylates such as trimethylolpropane trimethacrylate and neopentyl dimethacrylate have been known.

[Problems to be Solved by the Invention] However, with the conventional methods, a cured product having high elastic modulus and high strength could not be obtained.

To solve this problem, the present inventors developed a thermoplastic resin (
We filed an application for a composition consisting of meth)acrylate and, if necessary, a fiber component (Japanese Patent Application No. 1263548, Japanese Patent Application No. 1999).
-264322, Japanese Patent Application No. 1-264323).

However, although these cured products have a high modulus of elasticity and high strength, the impact resistance may be insufficient depending on the use of the molded product.

[Means for Solving the Problems] As a result of intensive studies by the present inventors on compositions from which cured products having high elastic modulus, high strength, and excellent impact resistance can be obtained, and methods for producing them, We have arrived at the present invention.

That is, the present invention provides a molding composition comprising a thermoplastic resin (A), a monofunctional and/or polyfunctional (meth)acrylate (B), and optionally a fiber component and a polymerization initiator. In this case, the polymerizable monomer (C) containing a polar group is at least 0.0% of (B).
A molding composition characterized by using 0.05% by weight, a composition with no fluidity, a molded article cured by heat and/or radiation irradiation, and a method for producing the same.

The thermoplastic resin (A) in the present invention is not particularly limited, but for example, vinyl chloride resin, ABSlMBS, NB
Examples include R, PMMA, polycaprolactone, saturated polyester, polyethylene, polypropylene, chlorinated polyolefin, and nylon, which can be used alone or in combination of two or more. Further, a thermosetting resin such as Evoquin resin, alkyd resin, etc. can be used in combination.

Among these, vinyl chloride resin is preferred.

Vinyl chloride resins include vinyl chloride homopolymer, vinyl chloride and other vinyl monomers, vinyl acetate, vinylidene chloride, acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate, vinyl propionate, etc. Examples include copolymers with unsaturated monomers and post-chlorinated products of these polymers.

Particularly preferred are vinyl chloride homopolymers and copolymers with a vinyl chloride content of 70% by weight or more.

The degree of polymerization of the vinyl chloride resin is not particularly limited, but is usually 300 to 10,000. Preferably 500-600
It is 0.

In the monofunctional and/or polyfunctional (meth)acrylate (B) in the present invention, (meth)acrylate refers to acrylate and methacrylate, and specifically, monofunctional (meth)acrylate includes, for example, (meth)acrylate. ) 2-ethylhexyl acrylate and 2
- Ethylhexanol, phenol, alkyl (the number of carbon atoms in the alkyl group is usually 1 to 20) phenol, and other alkylene oxides [ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as Po) and other coadducts ( Examples include (meth)acrylate (hereinafter abbreviated as AoA). In addition, examples of polyfunctional (meth)acrylates include 114-butylene glycol,
Examples include neopentyl glycol, 11 B-hexane glycol, bisphenol A1 hisphenol F, )limethylolpropane, pentaerythritol, dipentaerythritol, and (meth)acrylates of these AOAs.

Furthermore, (meth)acrylates having an alicyclic structure can also be used. Monofunctional (meth)acrylates having an alicyclic structure are not particularly limited, but include, for example, those described in Japanese Patent Application No. 1-265829.

In addition, the polyfunctional (meth)acrylate having an alicyclic structure is not particularly limited, but for example, general formula (1)
, (2) and (3).

→CH2)n-(0-A)qoOcc=cHa
(1)-(-CH2)n-(0-A)qOOC
C:C1]2 (2)I (wherein, R11Ra+ Rs is a hydrogen atom or a methyl group, A is an ethylene group or a propylene group, and ps
Q is an integer of 0 to 10, rrh n is an integer of 0 to 2, and Xs V is an integer of 0 to 3. ) In general formulas (1), (2) and (3), pl
q is preferably an integer of 0 to 5, ffh n is preferably an integer of 0 to 1, and Xs''l is preferably an integer of 0 to 2.

In addition, alicyclic polyisocyanates such as inphorone diisocyanate and dicyclohexyl diisocyanate and hydroxyl group-containing (meth)acrylates [for example, (meth)
2-hydroxyethyl acrylate, etc.] or (meth)
A reaction product with acrylic acid, a reaction product between an alicyclic polyan such as isophorone diamine or dicyclohexyl diamine, and (meth)acrylic acid chloride can also be used.

Particularly preferably, the compound represented by the general formula (1) is bis[(meth)acryloyloxycotricyclo[5
,2,1,0'・6]decane (pN msn, , (h
XN 'Y is 0), bis[(meth)acryloyloxymethylcotricyclo[5,2゜1,02
=al decane (ps Q% X1y is O, m1n
1), as a compound represented by general formula (2),
Bis[(meth)acryloyloxycotetracypho[
4,4,0,1'-'+ 1'・”] Dodecane (p
lrrh n1Q is 0 and X is 1), bis[(
meth)acryloyloxymethylcotetracyclo[4+
4+ O11'-', L"" cototecan (pl q is O, rnz , ns It is a (meth)acrylic acid ester of an adduct (pl q is 1 to 3).

These (meth)acrylates can be used alone or in combination of two or more.

The (meth)acrylate having an alicyclic structure in (B) is
They may be used alone or in combination of two or more, and the amount added is usually 5% by weight or more, preferably 10% by weight or more.

One polymerizable monomer containing a polar group (C
) are not particularly limited, and include hydroxyl group, carboxy group, amine group, phosphoric acid group (>P-OH), sulfonic acid group (-8O
Known materials containing at least one polar group such as IH) and salts thereof can be used.

Preferably, it is a polymerizable monomer containing a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

Examples of the polymerizable monomer containing a hydroxyl group include hydroxyalkyl (meth)acrylate (alkyl usually has 2 to 4 carbon atoms) and adducts thereof such as EO, PO and/or caprolactone. In addition, examples of polymerizable monomers containing carboxyl groups include:
Esterified products of (meth)acrylic acid, hydroxyalkyl (meth)acrylate and polybasic acids and/or their anhydrides [such as succinic acid mono(meth)acrylate and isophthalic acid mono(meth)acrylate] . Examples of the polymerizable monomer containing an amino group include dialkyl (usually has 1 to 4 carbon atoms) aminoalkyl (and usually has 2 to 4 carbon atoms) (meth)acrylates. Further, examples of the polymerizable monomer containing a phosphoric acid group include EOO phosphoric acid mono(meth)acrylate (hydrogen atom or methyl group), EO-modified phosphoric acid mono(meth)acrylate (hydrogen atom or methyl group), and EO-modified phosphoric acid mono(meth)acrylate. In addition, as a polymerizable monomer containing a sulfonic acid group, for example, (meth)
Examples include acrylamide propane sulfonic acid.

The amount of (C) added is at least 0°05 of (B).
It is at least 1% by weight, preferably at least O, 1m1t%.

When the addition (C) (1) is less than 0.05% by weight, almost no effect of improving the impact resistance of the obtained cured product is observed.

In the present invention, the weight ratio of (A) and (B) is not particularly limited, but is usually 20:80 to 80:20, preferably 30:70 to 70:30.

When (A) is less than 20, the obtained cured product becomes brittle and 8
If it exceeds 0, the +7ij property and strength of the obtained cured product will decrease.

In the present invention, a fiber component may be added if necessary. The fiber component is not particularly limited as long as it is fibrous, but preferably glass, carbon, polyester,
Polyamide and polyimide. Particularly preferred are glass and carbon fibers. Additionally, surface-treated fiber components can also be used.

The shape of the fiber component is not particularly limited, but for example, in the case of glass fiber, chive strand, milled fiber roving cloth, cloth, chopped strand pine 1, huntinous strand mat, nonwoven fabric, etc. can be used, and preferably They are chopped strand, roving cloth, and chopped strand mat.

In order to obtain a fiber-reinforced molded article by blending the fiber component, the fiber component should be added in an amount of 1 part per 100 parts of the total weight of (A) and (B).
It is preferable to mix 5 parts or more.

In the present invention, a polymerization initiator, such as a known thermal and/or photopolymerization initiator, may be added if necessary. The amount added is usually 0 to 100 parts by weight of CB)
The amount is 10 parts by weight, preferably 0.05 to 5 parts by weight.

However, when curing is performed by irradiation with radiation other than ultraviolet rays (for example, electron beam, neutron beam, gamma green, etc.), addition of an initiator is usually not necessary.

Examples of the thermal polymerization initiator include benzoyl peroxide, dicumyl peroxide, 1-butyl peroxybenzoate, methyl ethyl ketone peroxide, and azobisisobutyronitrile. Examples of the photopolymerization initiator include benzoin alkyl ether, benzyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-i-phenylpropan-1-one, and benzophenone.

When a thermal polymerization initiator is used, a known accelerator such as a metal soap such as cobalt naphthenate or a tertiary amine such as dimethylaniline may be used in combination, if necessary.

In the present invention, an internal mold release agent may be used if necessary. Internal mold release agents are not particularly limited, but include, for example, carboxylic acid metal salts, hydroxy fatty acid amides, bisamides, acidic phosphoric acid esters and their metal soaps, higher fatty acids, higher fatty acid esters, higher alcohols and their AOAs.

Examples include wax, mineral oil, alkylsiloxane, etc., and carboxylic acid metal salts are preferred.

Particularly preferred are unsubstituted or substituted higher fatty acids such as stearic acid, oleic acid, palmitic acid, lauric acid, lylunic acid, hydroxystearic acid and lithium, sodium, potassium, calcium, barium, magnesium, copper, zinc, aluminum, chromium. , iron, cobalt,
It is a higher fatty acid metal salt consisting of nickel, tin, lead, etc.

These can be used alone or in combination.

The blending ratio of the internal mold release agent is not particularly limited, but in the case of (A) and (B), it is usually 0.01 to 15 parts, preferably 0.02 to 10 parts per 11 parts and 0 parts of LL I O. be.

In addition, a filler may be added if necessary. There are no particular limitations on the filler, and known fillers can be added. For example, silicates [alumina silicate (clay, clay bentonite, feldspar, mica, etc.), hydrated alumina silicate (kaolin, waxite clay, etc.), magnesium silicate (talc, talcum, asbestos, etc.), calcium silicate, Pumice powder, etc., silicic acid (silica sand, quartz powder, diatomaceous earth, etc.), metal oxides (alumina, titanium oxide, magnesium oxide, zinc oxide, etc.), carbonates (calcium carbonate, barium carbonate, magnesium carbonate, etc.) , sulfates (barium sulfate, magnesium sulfate, etc.), hydroxides (calcium hydroxide, magnesium hydroxide, etc.), carbon (carbon black, graphite, etc.), and metal powders (iron powder, copper powder, aluminum powder, etc.). can give.

Further, in order to lower the specific gravity of the composition of the present invention, balloons such as glass balloons, shirasu balloons, and phenol balloons can be blended.

Further, if necessary, the composition of the present invention can be colored in a desired color by adding a known coloring pigment.

In addition, known additives for vinyl chloride resins such as stabilizers (metal soaps, epoxy stabilizers, organotin stabilizers, cadmium-barium stabilizers, lead salt stabilizers, etc.), surfactants, and colorants are also included. , a binder, a foaming agent, etc. can be added.

etc. can be added.

In addition, normal plasticizers for polyvinyl chloride resins (dioctyl phthalate, dioctyl adipate, etc.) can be added, but if the amount added is too large, it will be difficult to obtain a cured product with a high elastic modulus, so the amount added should be limited to the polyvinyl chloride resin. The amount is usually 30 parts by weight or less, preferably 20 parts by weight or less, per 100 parts.

The composition of the present invention can be plasticized by heating without substantially causing polymerization, and a composition that has no fluidity at room temperature can be obtained. Heating conditions are usually 40 to 120
℃, preferably 50 to 90℃.

The composition that has lost its fluidity can be molded by press molding, vacuum molding, or the like.

The composition of the present invention can be cured by heat and/or radiation. Note that radiation in the present invention refers to electron beams, neutron beams, gamma rays, ultraviolet rays, and the like.

Moreover, the method for producing a molded article using the composition of the present invention is not particularly limited. For example, the composition is placed in a mold at normal pressure,
Alternatively, a method in which the composition is injected and cured by applying pressure or under reduced pressure in a mold as necessary, or a composition in which the composition is made into a desired shape (for example, a sheet shape, a lump shape), or at the same time plasticized by heating to eliminate fluidity. Examples include a method in which an object is molded using a mold or the like and then hardened. As a specific example,
Examples include cast molding, injection molding, reaction molding, resin injection molding, compression molding, extrusion molding, and transfer molding.

[Example] The present invention will be explained below using Examples, but the present invention is not limited thereto. Parts in Examples are by weight.

Example 1 Vinyl chloride resin (degree of polymerization 1650) 60 parts Bis(methacryloyloxymethyl)tricyclo[5,2,
1,02.6 Codecane 20 parts Neopentyl glycol dimethacrylate 40 parts EO-modified phosphoric acid monoacrylate 0.1 part t-butyl peroxybezoate 0. 4 parts and 0.6 parts of mercaptotin acetate (stabilizer) were blended and defoamed under reduced pressure to obtain a composition of the present invention. The mixture was poured into a mold made of two glass plates with a gap of 3 mm, cured by heating at 130° C. for 5 minutes, and removed from the mold to obtain a molded article of the present invention.

Example 2 Vinyl chloride resin (degree of polymerization 3500) 50 parts bis(acryloyloxymethyl)tricyclo[5,2,1
,02.6 Codecane 15 parts 1.6-hexanethiol dimethacrylate 30 parts Succinic acid monomethacrylate 5 parts Zinc stearate 0. 5 parts calcium stearate 0. 2 parts t-butyl peroxybenzoate 0. 5 parts mercaptotin diothylate 0. A composition of the present invention was obtained using 5 parts in the same manner as in Example 1.

This composition was poured into a mold made of two glass plates with a gap of 3 mm, and heated at 80° C. for 10 minutes to obtain a non-flowable composition. This composition was heated at 130°C and 50Kg/Cm.
A molded article of the present invention was obtained after press molding under the conditions of 2 for 5 minutes.

Example 3 Vinyl chloride resin (degree of polymerization 1650) 60 parts Bis(methacryloyloxymethyl)tricyclo[5,2,
1,0'.6 codecane 15 parts POA dimethacrylate of hydrogenated bisphenol A 15 parts neopentyl glycol dimethacrylate 40 parts EO-modified phosphoric acid monoacrylate 0. 5 parts zinc stearate 0.6 parts calcium stearate 0.3 parts t-butylbaroxybezoate 0.4 parts mercaptotin acetate
0.6 parts of glass fiber (length 25 mm)
impregnated with 100 parts of Cheetzbut strands to a thickness of approximately 4
A sheet-like composition of the present invention having a thickness of 1 mm was obtained. This composition was placed in a mold, heated and pressurized at 130° C. and 50 kg/cm′ for 5 minutes to obtain a fiber-reinforced molded article of the present invention.

Example 4 Vinyl chloride resin (degree of polymerization 3500) 25 parts bis(acryloyloxymethyl)tricyclo[5,2,0
2.6] Decane 25 parts EO-modified phosphoric acid monomethacrylate 2 parts Zinc stearate
0. 6 parts calcium stearate
o, 3 parts t-butyl peroxybenzoate 0
．． 5 parts mercaptotin diothylate 0.5
A composition of the present invention was obtained in the same manner as in Example 3 using 40 parts glass fiber and 20 parts carbonate.

This composition was heated at 80° C. for 10 minutes to obtain a composition with no fluidity. This composition was placed in a mold and heated to 130°C for 5 minutes.
The fiber-reinforced molded article of the present invention was obtained by heating and pressurizing under the conditions of , 30 kg/am2.

Comparative Example 1 A comparative composition was obtained by blending Example 1 except for the EO-modified phosphoric acid monoacrylate.

A molded body was obtained from this composition in the same manner as in Example 1.

Comparative Example 2 A comparative composition was obtained by blending Example 2 except for succinic acid monomethacrylate. A molded body was obtained from this composition in the same manner as in Example 2.

Comparative Example 3 A comparative composition was obtained by blending Example 3 except for the EO-modified phosphoric acid monoacrylate.

A molded body was obtained using this composition in the same manner as in Example 3.

Comparative Example 4 A comparative composition was obtained by blending Example 4 except for the EO-modified phosphoric acid monomethacrylate.

A molded body was obtained using this composition in the same manner as in Example 3.

Test Example 1 The impact resistance, flexural modulus, and flexural strength of the molded bodies obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were measured. The measurement results are shown in Table 1.

Table 1 (Note 1) Eyesight (with notch) Kg-01170m
2 [Effects of the Invention] The molded product produced using the composition of the present invention has high flexural modulus and bending strength, and has excellent impact resistance compared to conventional products.

Further, the composition of the present invention has the advantage that it has excellent adhesion to metals and the like.

The molded product obtained from the composition of the present invention has high impact resistance, modulus of elasticity, and high strength. etc.), electrical equipment such as housings (various insulation panels, switch boxes,
It can be used for parts such as supports, etc.), corrosion-resistant equipment (pump housings, tanks, waterproof pans, etc.), transportation equipment (front panels, fender bumpers, etc.), agricultural equipment, and other building materials.

Claims (1)

[Claims] 1. A molding material comprising a thermoplastic resin (A), a monofunctional and/or polyfunctional (meth)acrylate (B), and optionally a fiber component and a polymerization initiator. A molding composition characterized in that the composition contains at least 0.05% by weight of a polar group-containing polymerizable monomer (C) based on (B). 2. The composition according to claim 1, wherein (A) is a vinyl chloride resin. 3. The composition according to claim 1 or 2, wherein at least 5% by weight of (B) is a (meth)acrylate having an alicyclic structure. 4. (Meth)acrylate having an alicyclic structure has the general formula (
1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) The (meth)acrylate and/or general formula shown in (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) [In the formula, R_1 is hydrogen atom or methyl group, A is ethylene group or propylene group, p, q are integers of 0 to 10, m,
n is an integer of 0 to 2, and x and y are integers of 0 to 3. The composition according to claim 3, which is a (meth)acrylate represented by: 5. (Meth)acrylate having an alicyclic structure has the general formula (
3) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (3) [In the formula, R_1, R_2, R_3 are hydrogen atoms or methyl groups, A is ethylene group or propylene group, p and q are 0
It is an integer between ~10. The composition according to claim 3, which is a (meth)acrylate represented by: 6. The composition according to any one of claims 1 to 5, which has lost its fluidity through plasticization. 7. A method for producing a molding composition by heating the composition according to any one of claims 1 to 5 without substantially causing polymerization, thereby eliminating fluidity through plasticization. 8. A method for producing a molded article, which comprises heating and curing the composition according to any one of claims 1 to 6. 9. A method for producing a molded article, which comprises curing the composition according to any one of claims 1 to 6 by irradiation with radiation. 10. A molded article obtained by curing the composition according to any one of claims 1 to 6 with heat and/or radiation.