JPH03217410A - Molding composition and preparation of molded product - Google Patents

Abstract

PURPOSE:To provide the subject composition giving cured products each having high elastic modulus and high strength useful for preparing parts for business equipments and appliances by compounding a thermoplastic resin and the monofunctional and/or polyfunctional (meth)acrylate of specific composition as essential components. CONSTITUTION:The objective composition comprises essentially (A) a thermo plastic resin and (B) monofunctional and/or polyfunctional (meth)acrylates containing (i) >=5wt.% of a (meth)acrylate of formula I (R1 is H, CH3; A is ethylene, propylene; q ia 0-10) and (ii) >=5wt.% of a (meth)acrylate of formula II and/or formula III (m, n are 0-2; y is 0-3). The compound of formula I includes hydrogenated bisphenol A ethylene oxide adduct (meth)acrylate ester and the compound of formula II includes bis[(meth)acryloyloxy]tricyclo[5,2,0<2>,<6>]<decane.>.

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 glycol 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.

[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of extensive studies on compositions, molded bodies, and methods for producing the same that yield cured products with high elastic modulus and high strength.

That is, the present invention provides a molding composition containing a thermoplastic resin (A) and a monofunctional and/or polyfunctional (meth)acrylate (B) as essential components, in which (B), ■ General formula (1) I23 −+o−A) aoOc=cH2 l R+ (1) A (meth)acrylate represented by the formula (1) and (meth)acrylate represented by the general formula (2) (meth)acrylate [wherein RI is a hydrogen atom or a methyl group, A is an ethylene group or a brobylene group, p and q are 0 to 10
, rrh n is an integer of 0 to 2, and Xs'Y is an integer of 0 to 3. Molding compositions containing 5% by weight or more of (meth)acrylates represented by (1) and (2), compositions with no fluidity, molded bodies cured by heat and/or radiation irradiation, and the like. This is the manufacturing method.

The thermoplastic resin (A) in the present invention is not particularly limited, but for example, vinyl chloride resin, ABS1MBS, NB
Examples include R, PMMA, polycaprolactone, saturated polyester, polyethylene, polypropylene, chlorinated polyolefin, nylon, etc., 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 vinyl 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 io, preferably 500.
~6000.

The (meth)acrylate (B) in the present invention includes: (1) a methacrylate represented by the general formula (1), and (2) a methacrylate represented by the general formula (2) and/or a methacrylate represented by the general formula (3). Contains.

Note that (meth)acrylate as used in the present invention refers to acrylate and methacrylate.

Examples of the methacrylate represented by the general formula (1) include ethylene oxide adducts (hereinafter abbreviated as EOA) and/or propylene oxide adducts (hereinafter abbreviated as POA) of hydrogenated bisphenol A (3(p1 q
Examples include (meth)acrylic acid esters 1 to 3).

Examples of the (meth)acrylate represented by the general formula (2) include bis(meth)acryloyloxycotricyclo[5, 2. 0”・6 codecane (pN
rrh ns q1XN y is 0), bis[(meth)acryloyloxymethyl]trisic[5
, 2. 02.6] Decane (p1qX X%
7 is O and m'o n is 1).

Examples of the methacrylate represented by the general formula (3) include bis[(meth)acryloyloxycotetracyclo[4, 4, 0. 12・S, 17・1e
Codedecane (1) N m1nz Q is 0 and X is 1
), bis[(meth)acryloyloxymethylcotetracyclate[:4, 4, 0. 1j・5,
l, ?・19Cododecane (1) N q is 0 and ffh ns X is 1).

■Weight of (meth)acrylate represented by general formula (1) and ■(meth)acrylate represented by general formula (2) and/or (meth)acrylate represented by general formula (3) in (B) (1) and (2) are each 5% or more, preferably 10% or more.

In (B), (meth)acrylates other than general formula (1), general formula (2) and/or general formula (3) are not particularly limited, and known ones can be used.

Examples of monofunctional (meth)acrylates include 2-ethylhexyl (meth)acrylate and 2-ethylhexanol, phenol, alkylene oxides such as alkyl (the number of carbon atoms in the alkyl group is usually 1 to 20) phenol (for example, ethylene oxide), , propylene oxide, etc.) adducts (hereinafter abbreviated as AOA) (meth)
Examples include acrylate. Also, polyfunctional (meta)
Examples of acrylates include 1,4-butylene glycol, neobentyl glycol, 1, Ei-hexane glycol, bisphenol A1 bisphenol F1 trimethylolpropane, pentaerythritol, dipentaerythritol, and these AOAs (
Examples include meth)acrylates, and monofunctional (meth)acrylates having an alicyclic structure can also be used.

Although the monofunctional (meth)acrylate having an alicyclic structure is not particularly limited, for example, Japanese Patent Application No. 1-28582
Examples include those described in Specification No. 9.

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 when it exceeds 80, the elastic modulus and strength of the obtained cured product decrease.

In the present invention, a fiber component (C) may be blended if necessary. The fiber component is not particularly limited as long as it is fibrous, but preferably glass, carbon, polyester, polyamide, and 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, it is possible to use chive strand, milled fiber roving cloth, cloth, chopped strand mat, continuous strand mat, nonwoven fabric, etc., and preferably chopped strand, Roving cloth and chopped strand mat.

In order to obtain a fiber-reinforced molded article by blending (C), it is preferable to blend 15 parts or more of (C) with respect to 100 parts of the total weight of (A) and (B).

In the present invention, a polymerization initiator (D) such as a known thermal and/or photopolymerization initiator may be added if necessary. The amount added is usually 0 to 10 ff parts, preferably 0.05 to 5 parts by weight, per 1.00 parts by weight of (B). However, when curing by irradiation with radiation other than ultraviolet rays (e.g. electron beam, neutron beam, gamma ray, etc.),
Addition of initiator is usually not necessary.

Examples of the thermal polymerization initiator include penzoyl peroxide, dicumyl peroxide, t-butyl peroxypenzoate, methyl ethyl ketone peroxide, and azobisisobutyronitrile. Examples of the photopolymerization initiator include penzoin alkyl ether, benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylbroban-1-one, and penzophenone. can give.

In addition, when using a thermal polymerization initiator, 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 becomes 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 or less per 100 parts of polyvinyl chloride resin. , 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
°C1 Preferably it is 50 to 90°C.

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, the composition may be injected and cured under pressure or under reduced pressure in the mold, or after the composition has been formed into a desired shape (for example, a sheet or a block), or at the same time, it is plasticized by heating to eliminate fluidity. Examples include a method in which the composition is molded using a mold or the like and then cured. As a specific example,
Examples include cast molding, injection molding, reaction injection molding, resin injection, 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 1650) 60 parts EOA dimethacrylate of hydrogenated bisphenol A 15 parts Bis(
(methacrylicyloxymethyl) tricyclo[5, 2. 02.6] Decane 1
5 parts neopentyl glycol dimethacrylate 10 parts t-butyl baroxybezoate 0.4 parts merkabutotin acetate (stabilizer) 0.6 parts 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 POA dimethacrylate of hydrogenated bisphenol A 15 parts Bis(
Acryloyloxymethyl) trinculo [5, 2.
02.6 codecane 15 parts 1,6-hexanediol dimethacrylate 20 parts t-butynoleperoxybenzoate 0.5 parts mercaptotin acetate 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''G for 10 minutes to obtain a non-flowable composition.
The molded article of the present invention was obtained by press molding for 5 minutes under the conditions of g/cm2.

Example 3 Vinyl chloride resin (degree of polymerization IE350) 60 parts Hydrogenated bisphenol A POA dimethacrylate 10 parts Bis(
Methacryloxymethyl) Trisicyloxymethyl [5, 2. 02.6 Codecane 1
5 parts trimethylolpropane triacrylate 15 parts t-
0.4 parts of butyl baroxybezoate and 0.6 parts of mercaptotin acetate (stabilizer) were blended and impregnated into 30 parts of glass fiber (25 mm long Chiyo Sopdo strand) to form a sheet approximately 4 mm thick. A composition of the present invention was obtained. This composition was placed in a mold and heated at 130°CN50 for 5 minutes.
The fiber-reinforced molded article of the present invention was obtained by heating and pressurizing under the conditions of K g/cm 2 .

Example 4 Vinyl chloride resin (degree of polymerization 3500) - 50 parts hydrogenated bisphenol A dimethacrylate of POA 15 parts bis(
acryloyloxymethyl)tricyclo[:5, 2
．． 02.6 Codecane 10 parts Neopentyl glycol dimethacrylate 25 parts t-butylbaroxybenzoate} 0.5 parts Mercabuttin acetate 0. 5 parts glass fiber
A composition of the present invention was obtained using 30 parts in the same manner as in Example 3.

This composition was heated at 80'C1 for 10 minutes to obtain a non-flowable composition. Pour this composition into the mold and press for 13 minutes for 5 minutes.
A fiber-reinforced molded article of the present invention was obtained by heating and pressurizing under the conditions of 0° C1 and 30 Kg/cm2.

Comparative Example 1 Vinyl chloride resin (degree of polymerization 1650) E30 parts bis(methacrylicyloxymethyl) trisicyl[5, 2. 02.6 Codecane 3
0 parts neopentyl glycol dimethacrylate 10 parts t-butyl peroxybezoate 0.4 parts Mercabutin tin acetate (stabilizer) 0.6 parts were blended and foamed under reduced pressure to obtain a comparative composition. Example 1 A molded body was obtained in the same manner as above.

Comparative Example 2 Vinyl chloride resin (degree of polymerization 3500) 50 parts POA dimethacrylate of hydrogenated bisphenol A 30 parts 1,6
- 20 parts of hexanediol dimethacrylate 0.5 parts of t-butylperoxybenzoate 0.5 parts of mercaptotin acetate were blended and foamed under reduced pressure to obtain a comparative composition, and a molded body was obtained in the same manner as in Example 2. Ta.

Comparative Example 3 Vinyl chloride resin (degree of polymerization 1650) 60 parts Bis(methacrylicyloxymethyl) Trisicyl[5, 2. 02.6 Codecane 2
5-part trimethylolpropane triacrylate
1 5 parts t-butyl peroxybezoate 0. 0.6 parts of 4 parts mercaptotin acetate (stabilizer) was blended and foamed under reduced pressure to obtain a comparative composition, and a molded body was obtained in the same manner as in Example 3.

Comparative Example 4 Vinyl chloride resin (degree of polymerization 3500) 50 parts POA dimethacrylate of hydrogenated bisphenol A 15 parts Bis(
acryloyloxymethyl)tricyclo[5. 2.
02.6 Codecane 10 parts Neopentyl glycol dimethacrylate 25 parts t-butyl baroxybenzoate 0.5 part Mercabutin tin acetate 0.5 part Glass fiber
A comparative composition was obtained by blending 30 parts and defoaming under reduced pressure, and a molded body was obtained in the same manner as in Example 4.

Test Example 1 The 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 [Effects of the Invention] Molded bodies produced using the composition of the present invention have a higher elastic modulus and higher strength than conventional ones.

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. A molding composition containing a thermoplastic resin (A) and a monofunctional and/or polyfunctional (meth)acrylate (B) as essential components, in which (1) general Formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) (Meth) acrylate shown by (2) General formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) (Meth)acrylate and/or General formula (3) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(3) (In the formula, R_1 is a hydrogen atom or a methyl group, A is an ethylene group or 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. A molding composition containing 5% by weight or more of each of (1) and (2). 2. The composition according to claim 1, wherein (A) is a vinyl chloride resin. 3. The composition according to claim 1 or 2, which has lost its fluidity through plasticization. 4. A method for producing a molding composition, which comprises heating the composition according to claim 1 or 2 without substantially causing polymerization, thereby eliminating fluidity through plasticization. 5. A method for producing a molded article by heating and curing the composition according to any one of claims 1 to 3. 6. A method for producing a molded article, which comprises curing the composition according to any one of claims 1 to 3 by irradiation with radiation. 7. A molded article obtained by curing the composition according to any one of claims 1 to 3 with heat and/or radiation.