JPH03217403A - Molding composition and preparation of molded product - Google Patents

Abstract

PURPOSE:To provide the subject composition giving a molded product having high hardness and high strength and readily demoldable to shorten the molding cycle by compounding a thermoplastic resin, a functional (meth)acrylate, an inner mold release agent, etc. CONSTITUTION:The objective composition comprises the components selected from a group consisting of (A) a thermoplastic resin (preferably vinyl chloride resin), (B) a monofunctional and/or polyfunctional (meth)acrylate [preferably (meth)acrylate of formula I, II or III (R1-R3 are H, methyl; A is ethylene, propylene; p, q are 0-10; m, n are 0-2; x, y are 0-3)], (C) an inner mold release agent (preferably calcium stearate) and, if necessary, (D) a fiber material (preferably glass fiber or carbon fiber) and (E) a polymerization initiator (e.g. benzoyl peroxide or benzoin alkyl ether).

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 neopentynoreglycol 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 (
An application was filed for a composition consisting of meth)acrylate and, if necessary, a fiber component (Patent Application No. 1-2 6 3 5 4 8)
No., Japanese Patent Application No. 1-2434322 and Japanese Patent Application No. 1-2
8 4 3 2 3 specification).

However, these products can produce cured products with high elastic modulus and high strength, but when molded into a molded product using a mold, etc.
In order to make molding easier, it was necessary to apply a mold release agent to the mold.

[Means for Solving the Problems] The inventors of the present invention have conducted intensive studies on strings, molded objects, and methods for manufacturing them that can be easily molded from a mold without applying a mold release agent to the mold. We have arrived at the present invention.

That is, the present invention comprises a thermoplastic resin (A), a monofunctional and/or polyfunctional (meth)acrylate (B), an internal mold release agent (C), and if necessary a fiber component (D) and a polymerization initiator (E). ) and non-flowable compositions, heat and/or
Alternatively, it is a molded article cured by radiation irradiation and a method for producing the same.

The thermoplastic resin (A) in the present invention is not particularly limited, but includes, for example, vinyl chloride resin, ABS, MBS1N
Examples include BR, PMMA, polycaprolactone, saturated polyester, polyethylene, polypropylene, chlorinated polyolefin, and nylon, and they can be used alone or in combination of two or more.

Further, thermosetting resins such as epoxy resins and alkyd resins can be used in combination.

Among these, vinyl chloride resin is preferred.

Vinyl chloride-based resins include vinyl chloride homopolymers, or vinyl chloride and other monomers such as unsaturated vinyl acetate, vinylidene chloride, acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate, and vinyl propionate. Examples include copolymers with 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 10000, preferably 500 to
It's ooo.

The monofunctional and/or polyfunctional (meth)acrylate (B) in the present invention represents acrylate and methacrylate, and known ones can be used. Monofunctional (meta)
Examples of acrylates include 2-ethylhexyl (meth)acrylate and 2-ethylhexanol,
Phenol, alkyl (the number of carbon atoms in the alkyl group is usually 1 to
20) Alkylene oxides such as phenol (e.g. ethylene oxide, propylene oxide, etc.)
Examples include (meth)acrylate of an adduct (hereinafter abbreviated as AOA). In addition, examples of polyfunctional (meth)acrylates include 1,4-butylene glycol,
Examples include neoventinole glycol, 1,6-hexane glycol, bisphenol A1, bisphenol F1, trimethylonolepropane, 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).

R1 (wherein Rll R21 Rs is a hydrogen atom or a methyl group, A is an ethylene group or a brobylene group,
p1 q is an integer from 0 to 10, m1 n is an integer from 0 to 2,
X1 V is an integer from O to 3. ) In general formulas (1), (2) and (3), p1
q is preferably an integer of 0 to 5, ms n is preferably an integer of 0 to 1, and X1 y is preferably an integer of 0 to 2.

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

Particularly preferably, the compound represented by the general formula (1) is bis[(meth)acryloyloxycotrisictff
[5, 2. 02.6 codecane (Th m1
n1QN XN Y is 0), bis[(meta)
Acryloyloxymethylcotricyclo[:5, 2
, O”・6]decane (pN Q% XN Y
is 0 and Illlb n is 1), general formula (2)
As a compound represented by bis[(meth)acryloyloxycottetracyclo[4, 4, 0. 12
・5 17・Ill] Dodecane (psms n1Q
is 0 and X is 1), bis[(meth)acryloyloxymethyl]tetracyclo[4, 4, 0.
12・s, 1, T・l cododecane (1) zq
is O and m1nz ) is an acrylic ester.

(Meth)acrylates containing these alicyclic structures are
They can be used alone or in combination of two or more. When used in combination, for example, (meth)acrylate represented by general formula (1) and (meth)acrylate represented by general formula (3)
meth)acrylate, (meth)acrylate represented by general formula (2)
Acrylate and (meth)acrylate represented by general formula (3), (meth)acrylate represented by general formula (1) and (meth)acrylate represented by general formula (2), and (meth)acrylate represented by general formula (3) Combinations such as meth)acrylates are preferred.

The amount of (meth)acrylate having an alicyclic structure in (B) is usually 5% by weight or more, preferably 10% by weight or more. When used together, the amounts of (meth)acrylate represented by general formula (1) and/or (meth)acrylate represented by general formula (2) and (meth)acrylate represented by general formula (3) are usually Each amount is 5% by weight or more.

In the present invention, the internal mold release agent (C) is not particularly limited, but includes, for example, carboxylic acid metal salts, hydroxy fatty acid amides, bisamides, acidic phosphoric acid esters or metal soaps thereof,
Examples include higher fatty acids, higher fatty acid esters, higher alcohols or their A O A1 waxes, mineral oils, alkylsiloxanes, 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, linoleic acid, hydroxystearic acid and lithium, sodium, potassium, calcium, barium, magnesium, copper, zinc, aluminum, chromium. , a higher fatty acid metal salt consisting of iron, cobalt, nickel, tin, lead, etc.

(C) can be used alone or in combination.

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.

If (A) does not have a groove of 20, the obtained cured product will become brittle.
If it exceeds 0, the elastic modulus and strength of the obtained cured product will decrease.

In the present invention, the blending ratio of (C) is not particularly limited, but is usually 0.01 to 15 s1, preferably 0.02 to 10 parts per 100 parts of the total weight of (A) and CB).
Department.

In the present invention, a fiber component (D) may be blended if necessary. The fiber component is not particularly limited as long as it is fibrous, but preferably glass, carbon, polyester, polyamide, or polyimide. Particularly preferably,
Glass and carbon fiber. 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, chimney strands, milled fiber roving cloth, cloth, chipped strand mats, continuous strand mats, nonwoven fabrics, etc. can be used, and chopped strand mats, nonwoven fabrics, etc. can be used. They are strand, roving cloth, and chilled strand mat.

In order to obtain a fiber-reinforced molded product by blending (D), (D) must be added to the total weight of (A), (B), and (C) at 100%.
It is preferable to add 15 parts or more per part.

In the present invention, a polymerization initiator (E) such as a known thermal and/or photopolymerization initiator may be added if necessary. The amount added is usually 0 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on the weight part of (B) Zoo. However, radiation other than ultraviolet rays (e.g., electron beams,
When curing by irradiation (neutron beam, gamma ray, etc.), addition of an initiator is usually not necessary.

Examples of the thermal polymerization initiator include penzoyl peroxide, dicumyl peroxide, 1-butyl peroxybenzoate, methylethyl ketone peroxide, and azobisisobutyronitrile.

In addition, examples of the photopolymerization initiator include bezoin anolequinoleate, pendyl ketal, 1-hydroxy-hexylphenyl ketone, and 2-hydroxy-
Examples include 2-methyl-1-7enylpropan-1-one and besophenone.

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.

Further, known additives for vinyl chloride resins such as stabilizers, fillers, colorants, surfactants, thickeners, blowing agents, etc. can be added. Ordinary plasticizers for vinyl chloride resins can also be added, but if the amount added is too large, it becomes difficult to obtain a cured product with a high elastic modulus, so the amount added is usually 30 parts by weight per 100 parts of polyvinyl chloride resin. The amount is preferably 20 parts by weight or less.

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, reactor injection molding, resin injection molding, compression molding, extrusion molding, and transfer molding.

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

Example 1 Vinyl chloride resin (degree of polymerization 1850) EiO bis(methacryloyloxymethyl) trisic [:5, 2. 02.6 Codecane
20 parts neobentyl glycol dimethacrylate 20 parts zinc stearate 0.6 parts t-butyl peroxybezoate 0.4 parts Mercabutin tin acetate (stabilizer) 0.8 parts were blended, foamed under reduced pressure, and the composition of the present invention was prepared. A composition was obtained. 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. Furthermore, injection hardening was repeated five times using the same mold, and the mold was easily formed.

Example 2 Vinyl chloride resin (degree of polymerization 3500) 50 parts bis(acryloyloxymethyl)tricyclo[5,2
, O"・6] Decane 30 parts 1. 6-hexanediol dimethacrylate 20 parts Zinc stearate 0.5 part Calcium stearate 0.2 part t--f Tinoleperoxybenzoate} 0.5 part 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 to 130℃ and 50Kg/cm.
A molded article of the present invention was obtained after press molding for 5 minutes under the following conditions.Furthermore, press molding was performed 20 times using the same mold, and the molding was easily completed in all cases.

Example 3 Vinyl chloride resin (degree of polymerization 1850) 80 parts bis(methacrylicyloxymethyl) trisicol[5. 2t Q11. ll codecane
40 parts zinc stearate o.
Part e: 0.3 parts of calcium stearate, 0.4 parts of t-butyl baroxybezoate, 0.6 parts of mercaptotin acetate, and impregnated into 30 parts of glass fiber (chopped strands with a length of 25 mm) to a thickness of about 4 mm. A sheet-like composition of the present invention was obtained. This composition was put into a mold, heated at 130℃ for 5 minutes, and weighed 50Kg.
The fiber-reinforced molded article of the present invention was obtained by heating and pressing under the conditions of /cm2. Further pressing was performed 20 times using the same mold, and all the presses came out easily.

Example 4 Vinyl chloride resin (degree of polymerization 3500) 25 parts bis(acryloyloxymethyl)tricyclo[:5,
2. 02.6 Codecane 25 parts Zinc stearate 0. 6 parts calcium stearate 0.3 parts t-butyl baroxybenzoate 0. 5 parts mercaptotin diothylate 0.5 parts glass fiber
30 parts calcium carbonate (filler)
A composition of the present invention was obtained using 20 parts in the same manner as in Example 3.

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/cm2. Further pressing was performed 20 times using the same mold, but the mold was easily demolded in all cases.

Example 5 Vinyl chloride resin (degree of polymerization 1650) EiO part EOA dimethacrylate of hydrogenated bisphenol A 15 parts bis(
methacryloyloxymethyl) trisic [5, 2. 02.6 Codecane 1
5 parts neopentyl glycol dimethacrylate 10 parts zinc stearate 0.6 parts t-butyl baroxybezoate 0.4 parts Mercaptotin acetate (stabilizer) 0.6 parts were added in the same manner as in Example 1 to prepare the present invention. A composition was obtained.

This composition was treated in the same manner as in Example 1 to obtain a molded article of the present invention. Furthermore, injection hardening was repeated five times using the same mold, but
All were easily demolded.

Example 8 Vinyl chloride resin (degree of polymerization 3500) 50 parts Hydrogenated bisphenol A POA dimethacrylate 15 parts Bis(
acryloyloxymethyl)tricyclo[5, 2.
02.6 Codecane 15 parts 1,6-hexanediol dimethacrylate 20 parts Zinc stearate 0.5 parts Calcium stearate 0.2 parts t-Butyl baroxybenzoate 0. A composition of the present invention was obtained in the same manner as in Example 1 using 5 parts of mercaptotin acetate and 0.5 parts.

This composition was treated in the same manner as in Example 4 to obtain a non-flowable composition. This composition was treated in the same manner as in Example 4 to obtain a molded article of the present invention. I pressed the same mold 20 more times, but
Everything came easily to me.

Example 7 Vinyl chloride resin (degree of polymerization 1650) 25 parts POA dimethacrylate of hydrogenated bisphenol A 5 parts Bis(
(methacrylicyloxymethyl) tricyclo[5, 2. 02.6] Deccan
5-part trimethylolpropane triacrylate
1 5 parts Zinc stearate 0. 5 parts Calcium stearate 0.2 parts t-butyl baroxybezoate 0.3 parts Mercaptotin acetate (stabilizer) 0.3 parts Glass fiber
A composition of the present invention was obtained in the same manner as in Example 4 using 30 parts of calcium carbonate and 20 parts.

This composition was used in the same manner as in Example 4 to obtain a fiber-reinforced molded article of the present invention. I pressed the same mold 20 more times, but
Everything came easily to me.

Comparative Example 1 Vinyl chloride resin (degree of polymerization 1650) 60 parts Neopentyl glycol dimethacrylate 40 parts Zinc stearate o. A comparative composition was obtained in the same manner as in Example 1 except that part e was 0.4 parts of t-butyl baroxybezoate and 0.6 parts of mercabutin acetate (stabilizer).

A molded article for comparison was obtained using this composition in the same manner as in Example 1.

Comparative Example 2 Vinyl chloride resin (degree of polymerization 3500) 50 parts trimethylolpropane triacrylate
3 0 parts 1,6-hexanediol dimethacrylate 20 parts Zinc stearate 0.5 parts Calcium stearate 0.2 parts t-Butyl peroxybenzoate 0. A comparative composition was obtained in the same manner as in Example 1 except that 0.5 parts of mercaptotin diothylate were added.

This composition was treated in the same manner as in Example 2 to obtain a non-flowable composition for comparison. A comparative molded article was obtained using this composition in the same manner as in Example 2.

Comparative Example 3 Vinyl chloride resin (degree of polymerization 1650) 60 parts Neobentyl glycol dimethacrylate 40 parts Zinc stearate 0.6 parts Calcium stearate o. a part t-butyl baroxybezoate 0.4 part mercaptotin acetate
0.6 part glass fiber
A comparative composition was obtained using 30 parts in the same manner as in Example 3.

This composition was used in the same manner as in Example 3 to obtain a fiber-reinforced molded article for comparison.

Comparative Example 4 Vinyl chloride resin (degree of polymerization 3500) 25 parts trimethylolpropane triacrylate
2 5 parts zinc stearate
0.6 parts calcium stearate
0.3 part t-butyl baroxybenzoate 0.5 part Mercabuttin diothylate 0.
A comparative composition was obtained in the same manner as in Example 3 using 5 parts glass fiber 30 parts calcium carbonate (filler) 20 parts.

This composition was treated in the same manner as in Example 4 to obtain a non-flowable composition. This composition was used in the same manner as in Example 4 to obtain a fiber-reinforced molded article for comparison.

Reference Example 1 A comparative composition was obtained by blending Example 1 with zinc stearate removed. A molded body was obtained from this composition in the same manner as in Example 1. The first time, I came with a theory, but after repeating it twice, it became difficult.

Reference Example 2 A comparative composition was obtained by blending Example 2 with zinc stearate and calcium stearate removed.

A molded body was obtained from this composition in the same manner as in Example 2. The first time, it came with a mold, but after repeating it twice, it became difficult to remove the mold.

Reference Example 3 A comparative composition was obtained by blending Example 3 with zinc stearate and calcium stearate removed.

A molded body was obtained using this composition in the same manner as in Example 3. The first time I tried it, I was able to follow the theory, but after repeating it four times, it became difficult.

Reference Example 4 A comparative composition was obtained by blending Example 4 with zinc stearate and calcium stearate removed.

A molded body was obtained using this composition in the same manner as in Example 3. The first time, I came out of the mold, but after repeating it three times, it became difficult to make the mold.

Test Example 1 The flexural modulus and flexural strength of the molded bodies obtained in Examples 1 to 7 and Examples 1 to 4 were measured. The measurement results are shown in Table 1.

Table 1 [Effects of the Invention] Molded bodies produced using the composition of the present invention have higher hardness and strength than conventional ones.

Furthermore, since it is easy to mold from the mold, there is an advantage that the molding cycle can be shortened when molded products are continuously molded.

The molded product obtained from the composition of the present invention has a high modulus of elasticity and high strength, so it is suitable for use in office equipment (typewriters).
printers, copiers, etc.), parts and housings for home appliances (TVs, stereos, VTRs, etc.), electrical equipment (various insulating panels, switch boxes, supports, etc.), corrosion-resistant equipment (pump housings, tanks, waterproof vanes, etc.) ), transportation equipment (front panels, fender bumpers, etc.), agricultural equipment, etc., and construction materials.

Claims (1)

[Claims] 1. Thermoplastic resin (A), monofunctional and/or polyfunctional (meth)acrylate (B), internal mold release agent (C), and if necessary, fiber component (D) and polymerization initiator A molding composition comprising a component selected from the group consisting of (E). 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) (Meth)acrylates shown by (1) and/or general formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (Meth)acrylates shown by [In the formula, R_1 is a hydrogen atom or a methyl group, A is an ethylene group or a propylene group, p and 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 any one of claims 1 to 3. 5. (Meth)acrylate having an alicyclic structure has the general formula (
3) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(3) (Meth)acrylate shown by 0
~10 integer. ] The composition according to any one of claims 1 to 3. 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, which comprises heating the composition according to any one of claims 1 to 5 without substantially causing polymerization, and 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. 3. 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.