JPH01249802A - Production of resin - Google Patents

Abstract

PURPOSE:To provide an internal strain-free resin in a good workability, by polymerizing a liquid containing monomers, oligomers or a mixture thereof comprising a bisallylic compound and a (meth)acrylic compound as essential components while the liquid is placed on a specific liquid. CONSTITUTION:A polymerizable liquid A containing monomers, oligomers or a mixture thereof comprising a bisallylic compound and/or (meth)acrylic compound as essential components is polymerized, while the liquid A is placed on a liquid B having a little solubility with the liquid A and a density larger than that of the liquid A. A mixture containing an aliphatic, alicyclic or aromatic dihydric alcohol bis(allyl carbonate) monomer of the formula (R is the residue of a dihydric alcohol; n or the average value of n is 1-10), an oligomer or a mixture thereof is preferable as the mixture in the liquid A.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing a resin, and more particularly to a method for producing a cured resin molding.

More specifically, bisallyl compounds and/or (
This invention relates to a method for producing a cured resin molded product that can produce a molded product with less distortion when polymerizing a polymerizable liquid material containing a monomer or oligomer containing a meth)acrylic compound as an essential component, or a mixture thereof.

<Conventional technology> Conventionally, diethylene glycol bisallyl carbonate,
When a monomer or oligomer such as methyl methacrylate is injected into a mold for cast polymerization, the volume shrinks during polymerization, so polymerization must be carried out while the shape of the mold follows this volume shrinkage.

For this reason, when polymerizing such monomers, etc., it is usual to apply pressure to the mold using an elastic gasket, an elastic sheet, etc., as disclosed in JP-A-57-207026. Polymerization is performed while the shape of the mold follows the volumetric shrinkage due to polymerization.

However, when polymerization is carried out using this method, stress is applied to the resin during polymerization from outside such as an elastic gasket or an elastic sheet, causing residual distortion in the formed resin.

In addition, when molding resin using a normal mold, when taking out the molded resin from the mold after molding,
It is often difficult to take out, and workability is poor, which poses a problem.

<Problems to be Solved by the Invention> The present invention solves the above-mentioned problems of the prior art and provides a polymerization method containing a monomer or oligomer containing a bisallyl compound and/or (meth)acrylic compound as an essential component, or a mixture thereof. To provide a resin manufacturing method which can obtain a molded product with little distortion and has good workability when a cured resin molded product is obtained by polymerizing a liquid material.

Means for Solving the Problems> The present invention provides bisallyl compounds and/or (meth)
Dissolving a polymerizable liquid material containing a monomer or oligomer or a mixture thereof [A] containing an acrylic compound as an essential component with a polymerizable liquid material containing the monomer or oligomer or a mixture thereof [A]. The monomer or oligomer or the mixture thereof is present on the liquid material [B] which has a lower density and has a density greater than the density of the polymerizable liquid material containing the monomer or oligomer or the mixture thereof [A]. [A]
Provided is a method for producing a resin, which comprises polymerizing a polymerizable liquid material containing: t In addition, the monomer or oligomer or the mixture thereof [A] has the following formula (a) (a) (wherein R is a residue of a dihydric alcohol, and the value of n or the average value of n is 1 to 1). 10, preferably 2 to 10), or a mixture thereof.

In the present invention, the monomers, oligomers, or mixtures thereof that contain bisallyl compounds and/or (meth)acrylic compounds as essential components include 7mers alone, oligomers alone, mixtures of monomers and oligomers, and 2 types of 10mers. It contains a mixture of the above, a mixture of two or more types of oligomers, or a mixture of 1 m or more of monomers and one or more types of oligomers.

Further, in the present invention, the polymer may be a homopolymer or a copolymer.

<Structure of the invention> The present invention will be explained in detail below.

FIG. 1 shows a preferred embodiment of the resin manufacturing method of the present invention.

The method for producing the resin of the present invention includes monomers or oligomers containing bisallyl compounds and/or (meth)acrylic compounds as essential components, or mixtures thereof [A
] (hereinafter referred to as [A]).As shown in FIG.
] into a liquid [B] that has a low solubility with the polymerizable liquid containing [A] and has a higher density than the density of the polymerizable liquid containing [A]. to polymerize a polymerizable liquid containing [A].

[A] polymerized by the polymerization method (curing method) of the present invention is
It is a monomer or oligomer, or a mixture thereof, containing a bisallyl compound and/or a (meth)acrylic compound as an essential component.

The bisallyl compound used in [A] is not particularly limited as long as it is a bisallyl compound, and examples thereof include sialylene of a nuclear halogen-substituted benzene dicarboxylic acid described in JP-A-59-45312. Copolymerizable composition with glycol diallyl carbonate [1],
1f of esters of nuclear halogen-substituted benzenedicarboxylic acids (for example, 2,4-dichloroterephthalic acid bisallyl ester, etc.) described in JP-A-59-8709! Above and above,
A copolymerizable composition with one or more radically polymerizable aromatic ring-containing monofunctional monomers (for example, phenyl methacrylate, etc.) having a refractive index of 1.55 or more as a homopolymer [■! ], one or more specific bisallyl carbonates or bisβ-methylallyl carbonates [e.g., 1,4-bis(hydroxyethoxy)benzene bisallyl carbonate, etc.] described in JP-A-59-8710, and a single A copolymerizable composition with one or more radically polymerizable aromatic ring-containing monofunctional monomers (for example, phenyl methacrylate, etc.) having a refractive index of 1.55 or more as a combined product [III Co, JP-A-Sho No. 59-96109, a monomer prepared by reacting a monool (e.g. 4-benzyl-phenol) with an unsaturated carboxylic acid (chloride) [e.g. acrylic acid (chloride)] and a homopolymer having a refractive index of 1 A copolymerizable composition with a radically polymerizable monomer (e.g. styrene) having a molecular weight of . Copolymerizable composition [acid diallyl ester) and a bifunctional monomer (e.g. tetrabromophthalic acid diallyl ester)]
V] Copolymerizable composition described in JP-A-59-184210 [VI], diethylene glycol bisallyl carbonate [■],
and aliphatic, cycloaliphatic or aromatic represented by the general formula (wherein R is the residue of a dihydric alcohol, and the value of n or the average value of n is 1 to 1o, preferably 2 to 10) A composition [■] containing monomer or oligomer of bis(allyl carbonate) of group dihydric alcohol or a mixture thereof (a) is mentioned.

In the case of [■], component (a) preferably has a molar ratio of diallyl carbonate and dihydric alcohol of 4:1 or less,
More preferably, the reaction product has a molar ratio of 2:1.

The dihydric alcohol is preferably ethylene glycol, 1.3-propanediol, 1.4-butanediol, 1.6-hexanediol, diethylene glycol, polyethylene glycol, dipropylene glycol, propylene glycol, neopentyl glycol, Trimethylbentanediol, cyclohexane dimetatool, bis(hydroxymethyl)tricyclodecane, 2.
One or more of 7-norbornediol, α, α′-xylene diol, 1,4-bis(hydroxyethoxybenzene) and 2°2-bis[4-(hydroxyethoxy)phenyl]propane may be used. preferable.

In addition, in the present invention, such bisallyl compounds include the following components (a'), (b) and (C
) A liquid composition of bis(allyl carbonate) [■'] containing
The description of Publication No. 214 is incorporated herein by reference.

Component (a') is an aliphatic, cycloaliphatic or cycloaliphatic compound represented by the formula: Oligomers or oligomer mixtures of the aromatic dihydric alcohol bis(allyl carbonate) (
However, in the above formula, the bis(allyl carbonate) monomer of the dihydric alcohol optionally contained in the oligomer is 50% by weight or less) 10 to 90% by weight, and component (b) is represented by the formula (formula where R' is a residue of a dihydric or trihydric alcohol, and n' is 2 or 3). (allyl carbonate) monomer or mixture, in which the bis(allyl carbonate) oligomer or poly(allyl carbonate) of a dihydric or trihydric alcohol optionally contained in the monomer or mixture is not more than 30% by weight; - allyl esters of aliphatic or aromatic dicarboxylic or tricarboxylic acids of the formula where R# is the residue of a dicarboxylic or tricarboxylic acid and n'' is 2 or 3, and triallyl cyanurate; and triallyl isocyanurate O to 90% by weight, component (C) consists of 0 to 30% by weight of an acrylic monomer or a vinyl monomer; The sum of is greater than 0.

Component (a') is preferably the product of the reaction of diallyl carbonate and dihydric alcohol in a molar ratio of less than 4:1, preferably 2:l, where the dihydric alcohol is ethylene glycol, 1,3-propane. Diol, 1.4-
Butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, dipropylene glycol, propylene glycol, neopentyl glycol, trimethylbentanediol, cyclohexane dimetatool, bis(hydroxymethyl)tricyclodecane, 2°7-norbornanediol , α,α'-xylene diol, 1,4-bis(hydroxyethoxybenzene), and 2,2-bis(4-(hydroxyethoxy)phenyl)propane.

Component (b) is a molar ratio of diallyl carbonate to dihydric or trihydric alcohol of 6:1 or more, preferably 12:1.
Preferably, the dihydric or trihydric alcohol is ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, dipropylene glycol. , propylene glycol, neopentyl glycol, trimethylbentanediol, cyclohexane dimetatool, bis(hydroxymethyl)tricyclodecane, 2,7-norbornanediol, α,α′-xylene diol, 1゜4-bis(hydroxyethoxybenzene) ), 2.2-bis(4-(hydroxyethoxy)phenyl)propane, trimethylolpropane, and tri(hydroxyethyl) isocyanurate.

In addition, component (b) includes diallyl phthalate, diallyl succinate, diallyl adipate, diallyl chlorendate,
Also suitable are diallyl glycolate, diallylnaphthalene dicarboxylate and triallylmeritate.

Furthermore, as component (C), 1 f! of vinyl acetate, vinyl benzoate, methyl methacrylate, phenyl methacrylate, methyl acrylate, methyl maleate, maleic anhydride, and vinylidene chloride is used. Or two or more types are preferable.

The polymerizable liquid containing [A] is preferably a bisallyl such as diethylene glycol bisallyl carbonate, 1.4 bis(hydroxyethoxy)benzene bisallyl carbonate, or 2,4-dichloroterephthalic acid bisallyl ester. Examples include copolymer compositions of compounds and vinyl monomers having an aromatic ring, such as phenyl methacrylate and benzyl methacrylate.

The (meth)acrylic compound used as [A] is not particularly limited, but mono(meth)acrylates and di(meth)acrylates represented by the following structural formulas are preferably used, but in particular di(meth)acrylates are preferably used. (Meth)acrylate is preferred.

CH2=CH-Co (OCH2CH2). -〇CH
3n=3~9 CH2=CHCOOCH2CH20COCH2CH2C
00HCH2=CHC0(OCH2CH2)2 0
(CH2) 3 CH3CH3 CH2=CCo (OCH2CH2). 0CH3n
=2~23 CH3 CH2=CCOOCH3 n=1~23 Shil-13 n'=9 CH2-CH-Co-0(CH2-CH20) nCo
-CH=CH2n=4~14 CH2=CH-Coo (CH2)s 0OC-CH
=CH2n≠1~9 L to i12'' -UIJ- (J-CH112-t,,rt-
shin2-u-shiLJ-shin=shin2 The polymerizable liquid material containing such [A] may contain a polymerization initiator.

In the present invention, when polymerizing the polymerizable liquid material containing [A], there are no particular restrictions on the polymerization initiator used as long as it does not adversely affect the transparency, color, or other properties of the resin to be formed. , a photopolymerization initiator, a thermal polymerization initiator, a combined photopolymerization initiator, and a thermal polymerization initiator.

In addition to photopolymerization initiators, photopolymerization initiators include electron beam and radiation polymerization initiators.

Examples of the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenyl-propan-1-one.

As a thermal polymerization initiator, peroxydicarbonates such as diisopropyl peroxydicarbonate, di-secandabutyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and tertiary butyl perbenzoate;
benzoyl peroxide, acetyl peroxide, t-
Butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, peroxybenzoic acid
Organic peroxides and inorganic peroxides such as t-butyl, lauroyl peroxide, diisopropyl peroxydicarbonate, methyl ethyl ketone peroxide, and diacyl peroxides, and radical initiation such as azobisisobutyronitrile and azobismethylisovaleronitrile. Examples include agents.

Examples of the photo/thermal polymerization initiator include the following formula: The following compounds are mentioned.

The amount of the polymerization initiator used is 0.1 to 10 wt%, preferably 1 to 6 wt%, based on the polymerizable liquid material containing [A].
%.

Further, other fillers may be added to the polymerizable liquid material containing [A] to the extent that the physical properties of the resulting polymer are not impaired.

For example, it is also possible to add unsaturated carboxylic acids such as maleic anhydride or silane coupling agents such as vinyltriethoxysilane in proportions of up to 10% by weight.

The density of the polymerizable liquid material containing [A] is not particularly limited, but is usually about 0.9 to 1.2 g/cm'.

In addition, as such a polymerizable liquid material containing [A], a prepolymer obtained by prepolymerizing the above-mentioned material using a polymerization initiator or the like to the extent that fluidity is maintained can also be suitably used.

In the polymerization method of the present invention, such a polymerizable liquid material containing [A] is mixed with [A] as shown in FIG.
has low solubility in a polymerizable liquid material containing [A
] The polymerizable liquid containing [A] is polymerized, preferably in the presence of a polymerization initiator.

There are no particular restrictions on the liquid substance [B] as long as it has low solubility with the polymerizable liquid substance containing [A] and has a density greater than that of the polymerizable liquid substance containing [A]. do not have.

In this case, the solubility of the liquid substance [B] with the polymerizable liquid substance contained in [A] should be kept low to the extent that it does not adversely affect the transparency, weather resistance, surface properties, etc. of the resin to be formed. For example, when expressed in terms of solubility, it is usually 5% or less, preferably 3% or less.

When the solubility is like this, favorable results are obtained especially in terms of the hardness of the resin surface.

In addition, the density of the liquid [B] is not particularly limited, but it is usually 1
41 or more, preferably about 1.1 to 1.5.

Preferred examples of such liquid material [B] include aqueous solutions of metal halides, sulfates, nitrates, etc., which have a density greater than that of the polymerizable liquid material containing the above-mentioned [A]. with the concentration of inorganic salt adjusted, or
Examples include metals that are liquid at room temperature, such as mercury.

In the polymerization method of the present invention, the polymerizable liquid material containing [A] has a low solubility with the polymerizable liquid material containing [A], and the density of the polymerizable liquid material containing [A] is low. This is a polymerization method in which polymerization is carried out in the presence of a liquid material [B] having a higher density.

Any method may be used to make the polymerizable liquid material containing [A] exist on the liquid material [B], but usually a polymerization initiator is added to the mold 10 containing the liquid material EBI. A polymerizable liquid material containing the above-mentioned [A] is injected.

The thus obtained [B
- Polymerize the polymerizable liquid material containing [A] in a system consisting of two layers of the polymerizable liquid material containing [A].

It is preferable to add each liquid in order of density as described above, but after pouring the polymerizable liquid containing [A] into the mold 10 first, be careful not to suspend the liquid between the liquids. Then, the liquid material [B] may be injected to form a polymerizable liquid material layer containing [A] on the liquid material [B].

As the mold 10 used in the polymerization method of the present invention, any commonly used mold such as glass, polyvinyl chloride, polyethylene resin, polypropylene resin, poly4-methyl-1-pentene resin, etc. can be used.

Further, the shape of the mold 10 may be appropriately selected depending on the shape of the object to be formed.

Polymerization can be carried out under various conditions depending on the composition of the polymerizable liquid material containing [A] and the polymerization initiator contained.

In thermal polymerization, it varies depending on the shape and size, but for example, it is placed in a heating tank and heated to 30 to 150' C1, preferably 40 to 12
It is preferable to heat at 0° C. for 0.5 to 72 hours, preferably 1 to 4 hours.

In photopolymerization, for example, 60 W/cm to 150 W/cm
under a high-pressure mercury lamp for 1 to 2 hours, preferably for 3 to 3 minutes.
The polymerization is preferably carried out at a temperature of 40 to 120°C, preferably 60 to 100°C.

The resin obtained by the polymerization method of the present invention has no optical distortion and can be widely used for optical lenses, transparent plates, rod-shaped transparent bodies, etc.

Further, it is easy to remove from the mold and has good workability.

<Example> The present invention will be specifically explained below using Examples.

(Example 1) In a beaker with an inner diameter of 15 cm, a liquid [B] with a density of 1
．． Add a magnesium chloride aqueous solution adjusted to 30% to a depth of 3 cm.
Furthermore, the following polymerizable liquid material containing [A] was injected to a layer thickness of 4 cm.

Polymerizable liquid material containing [A]-1 Diallyl carbonate and diethylene glycol were mixed in a molar ratio of 2:1 in the presence of sodium ethoxide in JP-A No. 5
6-133246 (30 wt% is diethylene glycol bisallyl carbonate, 70 wt% is oligocarbonate, n
=3~7)...55% by weight
Tris(hydroxyethyl) isocyanurate prepared by reacting diallyl carbonate and tris(hydroxyethyl) isocyanurate at a molar ratio of 12:1
Tris (allyl carbonate)...
・12.4% by weight diethylene glycol bisallyl carbonate
・・・ ・・・ 2 7
, 5% by weight vinyl acetate.
...5% by weight diisopropyl peroxydicarbonate ...2.5% by weight The beaker containing the two layers thus obtained was placed in an air oven and heated from 30°C to 90°C for 7 days. The temperature was raised stepwise over a period of days to complete the polymerization of the polymerizable liquid material-1 containing [A].

This product had a pencil hardness of 3H, a density of 1.336, and was sufficiently polymerized. Furthermore, when observed with a ballariscope, optical distortion was extremely small. Furthermore, it was easy to take out from the beaker, and the workability was good.

(Example 2) In a beaker with an inner diameter of 5 cm, a liquid material [B] with a density of 1.
A zinc chloride aqueous solution adjusted to a concentration of 29 was poured to a depth of about 3 cm, and the following polymerizable liquid containing [A] was injected to a layer thickness of 4 cm.

Polymerizable liquid material containing [A]-2 Prepared by reacting diallyl carbonate and diethylene glycol at a molar ratio of 2:1 in the presence of sodium ethoxide under the conditions described in JP-A-56-133246. (30 wt% is diethylene glycol, bisallyl carbonate, 70 wt% is oligocarbonate, n = 3 to 7) ......58 wt% diallyl carbonate and tris(hydroxyethyl) isocyanurate at a molar ratio of 12:1. Tris(allyl carbonate) of tris(hydroxyethyl) isocyanurate prepared by reacting...
・・13% by weight diethylene glycol bisallyl carbonate
...
... 2 911 Amount % diisobrobyl baroxydicarbonate 1...2.7% by weight The beaker containing the two layers thus obtained was placed in an air oven and heated at 40°C. The temperature was then raised stepwise to 80° C. for 5 hours to complete the polymerization of the polymerizable liquid material-2 containing [A].

This product had a pencil hardness of 3H, a density of 1.340, and was sufficiently polymerized. Furthermore, when observed with a ballariscope, optical distortion was extremely low.

Furthermore, it was easy to take out from the beaker, and the workability was good.

(Example 3) In a 50 mj2 beaker with an inner diameter of 5 cm, a magnesium chloride aqueous solution adjusted to a density of 1.28 was poured as liquid [B] to a depth of about 5 mm, and further, as a polymerizable liquid containing [A]. The following materials were injected to a layer thickness of 4 cm.

Polymerizable liquid material containing [A]-3 Monomer with a viscosity of 14 cps/25°C, a saponification value of 340, and a bromination of 93... 99, 5 Benzoyl peroxide... ...0.5% by weight The density of this product was 1.08.

The beaker containing the two layers thus obtained was placed in an air vent and heated at 85° C. for 5 hours.

The obtained resin had a pencil hardness of 3H on both the upper and lower surfaces and a density of 1.255. Furthermore, when observed with a ballariscope, optical distortion was extremely small. Furthermore, it was easy to take out from the beaker, and the workability was good.

From the above results, the effects of the present invention are clear.

<Effects of the Invention> According to the method for producing a resin of the present invention, when a monomer or oligomer or a mixture thereof containing a bisallyl compound and/or (meth)acrylic compound as an essential component is polymerized, no stress is applied from the outside during polymerization. Since the polymerization shrinkage proceeds evenly without adding, the internal strain of the resulting resin is extremely small.

Moreover, when the polymerized resin is removed from the mold, it is easy to remove and the workability is good.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing an example of the polymerization method of the present invention. Explanation of symbols 10...Mold FIG, 1

Claims (2)

[Claims] (1) A polymerizable liquid material containing a monomer or oligomer or a mixture thereof [A] containing a bisallyl compound and/or a (meth)acrylic compound as an essential component is converted into a polymerizable liquid containing the monomer or oligomer or a mixture thereof [A]. is present on the liquid material [B] which has low solubility in the polymerizable liquid material containing the monomer or oligomer or the mixture thereof [A] and which has a higher density than the density of the polymerizable liquid material containing the monomer or oligomer or the mixture thereof [A]. A method for producing a resin, comprising: polymerizing a polymerizable liquid material containing the monomer, oligomer, or mixture thereof [A]. (2) The monomer, oligomer, or mixture thereof [A] has the following formula (a) Formula (a) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is a residue of dihydric alcohol, or the average value of n is from 1 to 10, preferably from 2 to 10. The method for producing a resin according to claim 1, which comprises: