JP2884095B2 - Molded article composition and molded article - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a molding composition and a molded article.

[Prior Art] Conventionally, as a molding composition, a composition comprising a vinyl chloride resin and a (meth) acrylate such as trimethylolpropane trimethacrylate or neopentyl glycol dimethacrylate has been known.

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

As a solution to this, the present inventors have a high elastic modulus, a thermoplastic resin as a composition from which a cured product having high strength is obtained,
Application for a composition comprising (meth) acrylate and, if necessary, a fiber component (Japanese Patent Application No. 1-263548, Japanese Patent Application No.
264322 and Japanese Patent Application No. 1-264323).

However, these products can obtain cured products with high elastic modulus and high strength, but when molding a molded product with a mold or the like, apply a release agent to the mold to facilitate removal from the mold. I needed to.

Means for Solving the Problems The present inventors have intensively studied to obtain a composition and a molded body that can be easily released from a mold without applying a mold release agent to the mold, and as a result, have reached the present invention. did. That is, the present invention comprises a thermoplastic resin (A), a monofunctional (meth) acrylate and / or a polyfunctional (meth) acrylate (B), and an internal release agent (C).
Is a (meth) acrylate (B1) having an alicyclic structure, wherein the weight ratio of (A) :( B) is 20:80 to 80:20,
(C) is based on 100 parts of the total weight of (A) and (B)
0.01 to 15 parts of a molding composition; and (A), (B) and (C)
15 parts or more based on 100 parts by weight of the total amount of the above; Further, the polymerization initiator (E) is added in an amount of 1 part per 100 parts by weight of (B).
The composition as described above or described, containing not more than 0 parts by weight; the composition according to any one of the above-described items, which is further heated substantially without causing polymerization, and is molded to lose fluidity by plasticization. A molded article obtained by curing the composition according to any of the above into a desired shape by heating and / or irradiation with radiation.

In the present invention, the thermoplastic resin (A) is not particularly limited, but for example, a vinyl chloride resin, ABS, MBS, NBR, P
Examples thereof include MMA, polycaprolactone, saturated polyester, polyethylene, polypropylene, chlorinated polyolefin, and nylon, and two or more of them can be used in combination.

Of these, vinyl chloride resins are preferred. Examples of the vinyl chloride resin include vinyl chloride homopolymer or vinyl chloride and other vinyl monomers such as vinyl acetate, vinylidene chloride, acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate and vinyl propionate. Copolymers with saturated monomers and post-chlorinated products of these polymers are exemplified.

Particularly preferred are vinyl chloride homopolymers and copolymers having 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 1
0000, preferably 500-6000.

A thermosetting resin such as an epoxy resin or an alkyd resin can be used together with (A) if necessary.

In the present invention, the monofunctional (meth) acrylate and / or polyfunctional (meth) acrylate (B) refers to a monofunctional acrylate or methacrylate and / or a polyfunctional acrylate or methacrylate. At least 5% by weight of
A (meth) acrylate having an alicyclic structure (B1), but a monofunctional (meth) acrylate other than (B1) and / or
Alternatively, known polyfunctional (meth) acrylates (B2) can be used.

Among (B2), examples of the monofunctional (meth) acrylate other than (B1) include 2-ethylhexyl (meth) acrylate; 2-ethylhexanol, phenol, and alkyl (the alkyl group usually has 1 to 20 carbon atoms). ) Adducts of alkylene oxides such as phenol (eg, ethylene oxide, propylene oxide, etc.) (hereinafter AOA
(Abbreviated as (meth)) acrylate.

In (B2), examples of the polyfunctional (meth) acrylate other than (B1) include, for example, 1,4-butylene glycol, neopentyl glycol, 1,6-hexane glycol, bisphenol A, bisphenol F, and trimethylol. (Meth) acrylates of propane, pentaerythritol, dipentaerythritol or their AOA.

Further, among (B1), the monofunctional (meth) acrylate having an alicyclic structure is not particularly limited, and examples thereof include those described in Japanese Patent Application No. 1-265829.

Further, among (B1), the polyfunctional (meth) acrylate having an alicyclic structure is not particularly limited. For example, monomers represented by the following general formulas (1), (2) and (3) Is raised.

[In each of the formulas (1), (2) and (3), R ₁ , R ₂ and R ₃ are 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 and n are integers of 0 to 2,
x and y are integers of 0 to 3. In the general formulas (1), (2) and (3), p and q
Are preferably integers of 0 to 5, and m and n are preferably 0 to 1
And x and y are preferably integers of 0 to 2.

Further, an alicyclic polyisocyanate such as isophorone diisocyanate and dicyclohexylmethane diisocyanate and a hydroxyl group-containing (meth) acrylate [for example,
2-hydroxyethyl (meth) acrylate] or a reaction product with (meth) acrylic acid, isophorone diamine,
A reaction product of an alicyclic polyamine such as dicyclohexylmethanediamine and (meth) acrylic acid chloride can also be used.

Particularly preferably, as the compound represented by the general formula (1), bis [(meth) acryloyloxy] tricyclo [5,2,0 ^2.6 ] decane (p, m, n, q, x, y is 0) , Bis [(meth) acryloyloxymethyl] tricyclo [5,2,0 ^2.6 ] decane (p, q, x, y are 0,
m, n having 1) a compound represented by the general formula (2), bis [(meth) acryloyloxy] tetracyclo [4,0,1 ^2.5, 1 ^7.10] dodecane (p, m, n, q is 0
In, x is from of 1), bis [(meth) acryloyloxy methyl] tetracyclo [4,4,0,1 ^2.5, 1, ^7.10] dodecane (p, with q is 0, m, n, x is from 1 And (meth) acrylic acid esters of ethylene oxide and / or propylene oxide adducts of hydrogenated bisphenol A (p and q are 1 to 3) as compounds represented by the general formula (3).

(Meth) acrylates having these alicyclic structures are:
Two or more can be used in combination. When used in combination, for example, (meth) acrylate (B11) represented by the general formula (1) and (meth) acrylate (B1) represented by the general formula (3)
3) a (meth) acrylate represented by the general formula (2) (B
12) and (meth) acrylate (B13) represented by general formula (3), (meth) acrylate (B11) represented by general formula (1), and (meth) acrylate (B12) represented by general formula (2) And a combination of (meth) acrylate (B13) represented by the general formula (3) is preferable.

The amount of (meth) acrylate (B1) having an alicyclic structure in (B) is usually 5% by weight or more, preferably 10% by weight or more. (Meth) acrylate (B11) represented by the general formula (1) and / or (meth) acrylate (B12) represented by the general formula (2) and (meth) acrylate (B13) represented by the general formula (3) When both are used together, each is usually at least 5% by weight.

In the present invention, the internal release agent (C) is not particularly limited. For example, metal carboxylate, hydroxy fatty acid amide, bisamide, acidic phosphate or its metal soap, higher fatty acid, higher fatty acid ester, higher alcohol or AOA, Examples thereof include wax, mineral oil, and alkyl siloxane, and are preferably metal carboxylate.

Particularly preferably, stearic acid, oleic acid, palmitic acid, lauric acid, linoleic acid, unsubstituted or substituted higher fatty acids such as hydroxystearic acid and lithium,
It is a higher fatty acid metal salt composed of sodium, potassium, calcium, barium, magnesium, copper, zinc, aluminum, chromium, iron, cobalt, nickel, tin, lead and the like.

 (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) is less than 20, the obtained cured product becomes brittle and 80
If the ratio exceeds the above range, the elastic modulus and strength of the obtained cured product decrease.

In the present invention, the mixing ratio of (C) is not particularly limited, but is usually 0.01 to 15 parts, preferably 0.02 to 10 parts, based on 100 parts of the total weight of (A) and (B).

In the present invention, the fiber component (D) can be blended if necessary. The fiber component is not particularly limited as long as it is fibrous, but is preferably glass, carbon, polyester, polyamide, or polyimide. Particularly preferred are glass and carbon fibers. Further, a fiber component whose surface has been treated can also be used.

The shape of the fiber component is not particularly limited, but, for example, in the case of glass fiber, chopped strand, milled fiber, roving cloth, cloth, chopped strand mat, continuous strand mat, nonwoven fabric and the like can be used, and preferably chopped strand, roving Cross, chopped strand mat.

In order to obtain a fiber-reinforced molded body by blending (D), (D)
Is preferably blended in an amount of 15 parts or more based on 100 parts in total weight of (A), (B), and (C).

In the present invention, if necessary, a polymerization initiator (E), for example, a known thermal polymerization initiator and / or a light weight initiator can be added. The amount added is generally 0 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of (B). However, in the case of curing by irradiation with radiation other than ultraviolet rays (for example, electron beam, neutron beam, γ-ray, etc.), addition of an initiator is usually unnecessary.

Examples of the thermal polymerization initiator include benzoyl peroxide, dicumyl peroxide, t-butylperoxybenzoate, methyl ethyl ketone peroxide, and azobisisobutyronitrile.

Examples of the photopolymerization initiator include benzoin alkyl ether, benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one, benzophenone and the like can be mentioned.

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 can be used in combination, if necessary.

Further, known additives of the vinyl chloride resin such as a stabilizer, a filler, a coloring agent, a surfactant, a thickener, and a foaming agent can be added. Normal plasticizers for vinyl chloride resins can also be added, but if the addition amount is large, it becomes difficult to obtain a cured product having a high elastic modulus, so the addition amount is usually 30 parts by weight based on 100 parts of the polyvinyl chloride resin. Below, preferably 2
0 parts by weight or less.

The composition of the present invention can be further plasticized by heating without substantially causing polymerization to obtain a composition having no fluidity at room temperature. The heating conditions are usually 40
120120 ° C., preferably 50-90 ° C.

The composition having no fluidity can be molded by press molding, vacuum molding, or the like.

The composition of the present invention can be cured by heating and / or irradiation. The radiation in the present invention means an electron beam, a neutron beam, a γ-ray, an ultraviolet ray, or the like.

Further, the method for producing a molded article using the composition of the present invention is not particularly limited. For example, a method of curing the composition by injecting the composition into the mold at normal pressure or pressurized as necessary, or injecting the inside of the mold into reduced pressure, curing the composition into a desired shape (for example, a sheet or a lump), or simultaneously. A method in which a composition plasticized by heating to lose fluidity is molded in a mold or the like and then cured. Specific examples include cast molding, injection molding, reaction injection molding, resin injection, compression molding, extrusion molding, transfer molding and the like.

EXAMPLES Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto. Parts in Examples are parts by weight.

Example 1 Vinyl chloride resin (degree of polymerization 1650) 60 parts bis (methacryloyloxymethyl) tricyclo [5,
2,0 ^2.6 ] decane 20 parts Neopentyl glycol dimethacrylate 20 parts Zinc stearate 0.6 part t-butyl peroxybezoate 0.4 parts Mercaptotin acetate (stabilizer) 0.6 part is blended and defoamed under reduced pressure to form the composition of the present invention. I got something.

The mixture was poured into a mold made of two glass plates and having 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. Injection curing was repeated 5 times using the same mold, but all molds could be easily removed.

Example 2 Vinyl chloride resin (degree of polymerization: 3500) 50 parts bis (acryloyloxymethyl) tricyclo [5,2,
0 ^2.6 ] decane 30 parts 1,6-hexanediol dimethacrylate 20 parts Zinc stearate 0.5 parts Calcium stearate 0.2 parts t-butyl peroxybenzoate 0.5 parts Mercaptotin dithiolate 0.5 parts as in Example 1 I got something.

This composition was poured into a mold made of two glass plates and having a gap of 3 mm, and heated at 80 ° C. for 10 minutes to obtain a composition having no fluidity.

The composition 1 was press-molded at 130 ° C. and 50 kg / cm ² for 5 minutes and then released from the mold to obtain a molded article of the present invention. Further press molding was performed 20 times using the same mold, but all the molds could be easily removed.

Example 3 Vinyl chloride resin (degree of polymerization 1650) 60 parts bis (methacryloyloxymethyl) tricyclo [5,
2,0 ^2.6 ] decane 40 parts Zinc stearate 0.6 parts Calcium stearate 0.3 parts t-butyl peroxybezoate 0.4 parts Mercapto tin acetate 0.6 parts blended and impregnated into 30 parts of glass fiber (25 mm long chopped strand) Thus, a sheet-like composition of the present invention having a thickness of about 4 mm was obtained.

This composition was placed in a mold and heated and pressed at 130 ° C. and 50 kg / cm ² for 5 minutes to obtain a fiber-reinforced molded article of the present invention.
Pressing 20 more times with the same mold, all came off easily.

Example 4 Vinyl chloride resin (degree of polymerization: 3500) 25 parts bis (acryloyloxymethyl) tricyclo [5,2,
0 ^2.6 ] decane 25 parts Zinc stearate 0.6 parts Calcium stearate 0.3 parts t-butyl peroxybenzoate 0.5 parts Mercaptotin dithioate 0.5 parts Glass fiber 30 parts Calcium carbonate (filler) 20 parts Was obtained.

This composition was heated at 80 ° C. for 10 minutes to obtain a composition having no fluidity. Put this composition in a mold, 130 ° C, 30K for 5 minutes
The fiber-reinforced molded article of the present invention was obtained by heating and pressurizing under the conditions of g / cm ² . Pressing 20 more times using the same mold, all came off easily.

Example 5 Vinyl chloride resin (degree of polymerization: 1650) 60 parts EOA dimethacrylate of hydrogenated bisphenol A 15 parts Bis (methacryloyloxymethyl) tricyclo [5,
2,0 ^2.6 ] decane 15 parts Neopentyl glycol dimethacrylate 10 parts Zinc stearate 0.6 parts t-butyl peroxybezoate 0.4 parts Mercaptotin acetate (stabilizer) 0.6 parts A composition was obtained.

Using this composition, a molded article of the present invention was obtained in the same manner as in Example 1. Injection curing was repeated 5 times using the same mold, but all molds could be easily removed.

Example 6 Vinyl chloride resin (polymerization degree: 3500) 50 parts POA dimethacrylate of hydrogenated bisphenol A 15 parts Bis (acryloyloxymethyl) tricyclo [5,2,
0 ^2.6 ] decane 15 parts 1,6-hexanediol dimethacrylate 20 parts Zinc stearate 0.5 parts Calcium stearate 0.2 parts t-butyl peroxybenzoate 0.5 parts Mercaptotin acetate 0.5 parts as in Example 1 I got something.

Using this composition, a composition having no fluidity was obtained in the same manner as in Example 4. The composition of the present invention was obtained from this composition in the same manner as in Example 4. Pressing 20 more times using the same mold, all came off easily.

Example 7 Vinyl chloride resin (degree of polymerization 1650) 25 parts POA dimethacrylate of hydrogenated bisphenol A 5 parts Bis (methacryloyloxymethyl) tricyclo [5,
2,0 ^2.6 ] decane 5 parts Trimethylolpropane triacrylate 15 parts Zinc stearate 0.5 parts Calcium stearate 0.2 parts t-butyl peroxybezoate 0.3 parts Mercaptotin acetate (stabilizer) 0.3 parts Glass fiber 30 parts Calcium carbonate The composition of the present invention was obtained in the same manner as in Example 4 except for 20 parts.

Using this composition, a fiber-reinforced molded article of the present invention was obtained in the same manner as in Example 4. Furthermore, pressing was performed 20 times using the same mold, but all the molds could be easily removed.

Comparative Example 1 Vinyl chloride resin (degree of polymerization: 1650) 60 parts Neopentyl glycol dimethacrylate 40 parts Zinc stearate 0.6 parts t-butyl peroxybezoate 0.4 parts Mercaptotin acetate (stabilizer) 0.6 parts As in Example 1. To obtain a composition for comparison.

Using this composition, a molded article for comparison was obtained in the same manner as in Example 1.

Comparative Example 2 Vinyl chloride resin (degree of polymerization: 3500) 50 parts Trimethylolpropane triacrylate 30 parts 1,6-hexanediol dimethacrylate 20 parts Zinc stearate 0.5 parts Calcium stearate 0.2 parts t-butyl peroxybenzoate 0.5 parts Mercaptotin dithiolate 0.5 part was prepared in the same manner as in Example 1 to obtain a composition for comparison.

Using this composition, a composition having no fluidity for comparison was obtained in the same manner as in Example 2. Example 2 using this composition
A molded body for comparison was obtained in the same manner as described above.

Comparative Example 3 Vinyl chloride resin (degree of polymerization: 1650) 60 parts Neopentyl glycol dimethacrylate 40 parts Zinc stearate 0.6 parts Calcium stearate 0.3 parts t-butyl peroxybezoate 0.4 parts Mercapto tin acetate 0.6 parts Glass fiber 30 parts A composition for comparison was obtained in the same manner as in Example 3.

Using this composition, a fiber-reinforced molded article for comparison was obtained in the same manner as in Example 3.

Comparative Example 4 Vinyl chloride resin (degree of polymerization: 3500) 25 parts Trimethylolpropane triacrylate 25 parts Zinc stearate 0.6 parts Calcium stearate 0.3 parts t-butyl peroxybenzoate 0.5 parts Mercaptotin dithiolate 0.5 parts Glass fiber 30 parts Calcium carbonate (filled) Material) was used in the same manner as in Example 3 to obtain a comparative composition.

This composition was treated in the same manner as in Example 4 to obtain a composition having no fluidity. Using this composition, a fiber-reinforced molded article for comparison was obtained in the same manner as in Example 4.

Reference Example 1 A composition for comparison was obtained by blending Example 1 with the exception of zinc stearate. Example 1 using this composition
In the same manner as in the above, a molded body was obtained. For the first time, I was able to demold,
When repeated twice, demolding became difficult.

Reference Example 2 A composition for comparison was obtained by blending Example 2 with the exception of zinc stearate and calcium stearate. Using this composition, a molded article was obtained in the same manner as in Example 2. Demolding was able to be carried out the first time, but it was difficult to remove the mold twice.

Reference Example 3 A composition for comparison was obtained by blending Example 3 with the exception of zinc stearate and calcium stearate. Using this composition, a molded article was obtained in the same manner as in Example 3. The first time came with demolding, but when repeated four times, demolding became difficult.

Reference Example 4 A composition for comparison was obtained by blending Example 4 with the exception of zinc stearate and calcium stearate. A molded article was obtained from this composition in the same manner as in Example 3.
At the first time, demolding could be performed, but when repeated three times, demolding became difficult.

Test Example 1 The flexural modulus and bending strength of the molded articles obtained in Examples 1 to 7 and Examples 1 to 4 were measured. Table 1 shows the measurement results.
Shown in

[Effect of the Invention] A molded article produced by using the composition of the present invention has higher hardness and higher strength than a conventional one. Further, since the mold can be easily removed from the mold, there is an advantage that the molding cycle can be shortened in the case of continuous molding.

Since the molded article of the present invention obtained from the composition of the present invention has a high modulus of elasticity and high strength, it can be used for office equipment (typewriters, printers, copiers, etc.), home electric appliances (televisions, stereos, VTRs). Such as products, housings and other electrical equipment (various insulating panels, switch boxes,
It can be used for components such as support equipment, corrosion-resistant equipment (pump housing, tank, waterproof pan, etc.), transportation equipment (front panel, fender, bumper, etc.), agricultural equipment, and other building materials.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08F 2/44 CAS

Claims (7)

(57) [Claims] 1. A composition comprising a thermoplastic resin (A), a monofunctional (meth) acrylate and / or a polyfunctional (meth) acrylate (B), and an internal release agent (C), wherein at least 5% by weight in (B). Is a (meth) acrylate (B1) having an alicyclic structure, and the weight ratio of (A) :( B) is 20:80 to 80:
20, (C) is the total weight of (A) and (B) 100
The molding composition is 0.01 to 15 parts per part. 2. The composition according to claim 1, wherein the (meth) acrylate (B1) having an alicyclic structure is at least one (meth) acrylate represented by any of the following formulas (1) to (3). . [In each of the formulas (1), (2) and (3), R ₁ , R ₂ and R ₃ are 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 and n are integers of 0 to 2,
x and y are integers of 0 to 3. ] 3. The (meth) acrylate (B1) having an alicyclic structure has a (meth) acrylate (B11) represented by the general formula (1) and / or a (meth) acrylate (B12) represented by the general formula (2). ) And (meth) acrylate (B13) represented by the general formula (3), wherein at least 5% by weight of (B) is (B11) and / or (B1).
2. The composition according to claim 2, wherein at least 5% by weight of (B) is (B13). 4. The composition according to claim 1, further comprising 15 parts or more of the fiber component (D) based on 100 parts by weight of the total of (A), (B) and (C). 5. The method according to claim 1, wherein the polymerization initiator (E) is contained in an amount not exceeding 10 parts by weight per 100 parts by weight of (B).
The composition according to any one of the above. 6. A molding composition wherein the composition according to any one of claims 1 to 5 is heated without substantially causing polymerization to lose fluidity by plasticization. 7. A molded product obtained by curing the composition according to claim 1 into a desired shape by heating and / or irradiation.