JP2554403B2 - Transparent low shrinkage polymerized composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polymer composition which is transparent and has a low shrinkage ratio.

[0002]

2. Description of the Related Art Unsaturated polyester resin contains a radically polymerizable monomer such as styrene monomer, and therefore has a large shrinkage ratio of about 7% and is apt to be cracked especially at the time of high temperature molding. It has the drawback of being difficult. For this reason, it is usual to add a polymer such as polystyrene, polyvinyl acetate, polyolefin, polymethylmethacrylate, or a graft copolymer thereof to reduce the shrinkage rate.

[0003]

However, since these low-shrinking agents or non-shrinking agents are accompanied by phase separation, they are very excellent in terms of reduction in shrinkage, but on the other hand, the appearance after curing becomes opaque. , It becomes cloudy, and almost no rays of light pass through. Further, in the cured resin, after the thermoplastic resin is phase-separated at the time of high temperature molding, a void is generated due to the volume shrinkage during cooling, and the strength reduction is unavoidable. Especially in recent years
Demand is increasing in fields requiring a transparent appearance of a cured product such as artificial marble, and a low-shrinking agent which is transparent and has a low shrinkage factor and which does not lower mechanical strength has been demanded.

[0004]

[Wherein R is an organic residue derived from a divalent carboxylic acid having 2 to 18 carbon atoms, x is an integer of 2 to 6 and Z is 3 to 8 carbon atoms having x+1 hydroxyl group] Is an organic residue derived from a polyol consisting of B, and B is a divalent organic residue derived from a diol containing 2 to 20 carbon atoms. ]

The carbon number used as a raw material here is 2 to 18
The divalent carboxylic acid consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, β-methyladipic acid,
Pimelic acid, corkic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, 1,2- or 1,3- or 1,4-cyclohexanedicarboxylic acid,
Phthalic acid, isophthalic acid, terephthalic acid, diphenyl-
p,p'-dicarboxylic acid, diphenyl-m,m'-dicarboxylic acid, 1,4- or 1,5- or 2,6- or 2,7-naphthalene dicarboxylic acid, diphenylmethane-p,p'-dicarboxylic acid , Diphenylmethane-m,
m'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, p-phenylmethane-m,m'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, p-phenylenediacetic acid, p-carboxyphenylacetic acid , Methylterephthalic acid, tetrachlorophthalic acid and the like. Aromatic dicarboxylic acids having high symmetry, such as terephthalic acid and isophthalic acid, are particularly preferable for increasing Tg after curing.

Specific examples of the diol having 2 to 20 carbon atoms include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol and neopentyl. Glycol, 1,5-pentanediol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, undecamethylene glycol, dodecamethylene glycol, tridecamethylene glycol, eicosamethylene glycol, hydrogenation Bisphenol-A,
1,4-cyclohexanedimethanol, 2-ethyl-
Saturated glycol consisting of only carbon such as 2,5-pentanediol, 2-ethyl-1,3-hexanediol and styrene glycol, and ethylene oxide addition of diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol and bisphenol-A. Compounds, divalent saturated alcohols containing ether groups such as propylene oxide adducts of bisphenol-A, and glycols containing bromine such as dibromoneopentyl glycol.

Specific examples of the polyol having 3 to 8 carbon atoms include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and sorbitol.

If the crystallinity of these allyl ester oligomers is too high, they cannot be dissolved in the unsaturated polyester resin. Therefore, it is necessary to select a combination of raw materials so that the solubility is not so low, especially terephthalic acid or terephthalic acid. When a highly symmetrical dibasic acid such as 2,7-naphthalenedicarboxylic acid is used, it is better to use 1,2-propylene glycol, 1,3-butanediol or dipropylene glycol as the diol component. .. Also,
Neopentyl glycol, bisphenol-A ethylene oxide adduct, and bisphenol-A propylene oxide adduct are particularly excellent diols for suppressing hydrolysis of the ester group after curing.

Regarding the ratio of structure-A to structure-B, too much component of structure-B causes the viscosity after compounding to be too high and gelation to occur too easily. Is preferably at least 50 mol% or more, more preferably 66 mol% or more. Of course, only Structure-A can be used.

It is important to note that if the iodine value of the allyl ester oligomer to be blended is too high expressed by the Wis method, not only the curing of the unsaturated polyester will be significantly delayed but also curing with an allyl group such as styrene and curability will occur. When a monomer having a poor viscosity is used, there is a problem that the entire system becomes cloudy. On the other hand, if the iodine value is too low, phase separation will occur in the polyester portion during curing, resulting in an opaque cured product like an ordinary low-shrinking agent. It is desirable to select the iodine value of the polyallyl ester used therein from the range of 2 to 45, more preferably 10 to 40. If the iodine value is within this range, an allyl monomer produced as a by-product during the synthesis of the allyl ester oligomer may be mixed.

If the molecular weight is too small, the effect of low shrinkage is not exerted, and if it is too large, the solubility in the unsaturated polyester resin is lowered and the viscosity is increased, and in some cases, phase separation occurs after curing. There is a drawback that it causes white turbidity. Therefore, the molecular weight of the allyl ester oligomer to be used is preferably selected from the range of 1,000 to 50,000, more preferably 1500 to 20,000 in terms of polystyrene equivalent number average molecular weight measured by the GPC method.

As the effect of these allyl ester oligomers, since the molecular weight is appropriately high, the shrinkage rate after curing can be suppressed to a low level, and the allyl group at the terminal is copolymerized with the polyester resin, Does not become opaque without phase separation during curing. Also,
When the iodine value is within the above-specified range, it can be said to be an effective additive without causing curing inhibition as in the case where a diallyl phthalate (DAP) monomer is blended with an unsaturated polyester.

The unsaturated polyester to be blended here is a generally known one and is an unsaturated alkyd resin or vinyl ester dissolved in a radically polymerizable monomer.

As the unsaturated alkyd resin, various raw materials are known and it is difficult to exemplify them in a general manner. For example, a divalent unsaturated carboxylic acid derivative, a divalent saturated carboxylic acid derivative and a divalent polyol are used. An unsaturated alkyd synthesized by performing a dehydration reaction using

Examples of the divalent unsaturated carboxylic acid derivative used as a raw material include maleic anhydride, maleic acid, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and the like. Further, as the divalent saturated carboxylic acid derivative, succinic acid, glutaric acid, adipic acid, β-
Methyl adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, 1,2- or 1,3- or 1,4-cyclohexanedicarboxylic acid, Phthalic acid, isophthalic acid, terephthalic acid, 1,4- or 1,5- or 2,6- or 2,7-naphthalene dicarboxylic acid, methyl terephthalic acid, endic acid, chlorendic acid, tetrabromophthalic acid, tetrahydrophthalic acid Acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, phthalic anhydride, endic anhydride, chlorendic anhydride, tetrabromophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrate Hydrophthalic acid, methylhexahydrophthalic anhydride,
Examples thereof include dimethyl terephthalate, and as the divalent polyol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,5-pentanediol. , Hexamethylene glycol, heptamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, undecamethylene glycol, dodecamethylene glycol, tridecamethylene glycol, eicosamethylene glycol, hydrogenated bisphenol-A, 1,4-
Cyclohexanedimethanol, 2-ethyl-2,5-pentanediol, 2-ethyl-1,3-hexanediol, styrene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, bisphenol-A ethylene oxide adduct , Propylene oxide adduct of bisphenol-A, dibromoneopentyl glycol, diallyl ether of pentaerythritol, monoallyl ether of glycerin and the like.

The vinyl ester is a product obtained by reacting an epoxy resin with (meth)acrylic acid, which is also referred to as an epoxy acrylate. The epoxy resin used here is a bisphenol type, novolac type or aliphatic type. The type etc. are known. Regarding the physical properties of these synthetic methods and polymers after synthesis,
It is described in detail in books such as "Polyester Resin Handbook" (Eiichiro Takiyama, published by Nikkan Kogyo Shimbun).

Radical polymerizable monomers capable of dissolving these unsaturated alkyds and/or vinyl esters include styrene, vinyltoluene, α-methylstyrene,
Chlorostyrene, methyl methacrylate, ethyl acrylate, -n-butyl acrylate, 2-ethylhexyl acrylate, vinyl acetate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl isocyanurate, etc. It is present in a saturated alkyd or vinyl ester in an amount of about 20 to 50% by weight. Here, if the amount of the allyl ester oligomer compounded is too large, there is a drawback that the curing becomes slow and the viscosity becomes high, and it becomes difficult for the inorganic filler to enter. If the blending amount is too small, low shrinkage curing will not occur. Therefore, the total amount is 2 to 6
It is desirable to select from 0 part by weight, more preferably from 5 to 50 parts by weight.

As the initiator used for curing these compositions, any radical polymerization initiator can be used as long as it can generate radicals by heat, microwaves, infrared rays or ultraviolet rays. Therefore, it can be appropriately selected depending on the use and purpose of the curable composition, the compounding ratio of the components, the curing method, and the like.

Radical polymerization initiators that can be used in the polymerization by heat, microwave and infrared rays include, for example, 2,
Azo compounds such as 2'-azobisisobutyronitrile, 2,2-azobisisovaleronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide , Ketones such as cyclohexanone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, lauroyl peroxide and p-chlorobenzoyl peroxide. , 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene peroxide, cumene hydroperoxide, t-butyl peroxide and other hydroperoxides, dicumyl peroxide, t-butyl cumyl peroxide , The t
Dibutyl peroxides such as -butyl peroxide and tris(t-butylperoxy)triazine, 1,1
-Di-t-butylperoxycyclohexane, 2,2-
Peroxyketals such as di(t-butylperoxy)butane, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t- Butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, di- alkyl peresters such as t-butyl peroxytrimethyl adipate, diisopropyl peroxy dicarbonate,
Examples include parkanates such as di-sec-butylperoxydicarbonate and t-butylperoxyisopropylcarbonate.

Radical polymerization initiators that can be used in the polymerization by ultraviolet rays include, for example, acetophenone, 2,
2-dimethoxy-2-phenylacetophenone, 2,2
-Diethoxyacetophenone, 4'-isopropyl-2
-Hydroxy-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, 4,4'-bis(diethylamino)benzophenone, benzophenone,
Methyl(o-benzoyl)benzoate, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, benzoin , Benzoin methyl ether, benzoin ethyl ether,
Benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, benzyl,
Carbonyl compounds such as benzyl dimethyl ketal, benzyl diethyl ketal and diacetyl, anthraquinones or thioxanthone derivatives such as methylanthraquinone, chloroanthraquinone, chlorothioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone, sulfur compounds such as diphenyl disulfide and diothicabamate. can give.

The polymer composition of the present invention may be, as in the case of the conventional thermosetting resin composition, if desired, for example, a filler, a polymerization accelerator, a polymerization inhibitor, an internal release agent, a coupling agent,
By using a pigment, a flame retardant, and other additives in an amount that does not impair the characteristics of the composition, the molding processability or the physical properties of the molded article can be improved.

As the molding method of the composition of the present invention, the known molding methods and molding conditions similar to those of conventional thermosetting resins can be applied as they are. That is, a casting method in which the composition of the present invention is poured into a mold and cured, an injection molding method or a transfer molding method in which the composition is heated to be in a fluid state, and the composition is put into a mold and heat-cured, the composition A compression molding method in which a product is heated and pressed to be cured in a mold, the composition is dissolved in an appropriate organic solvent,
A laminated sheet molding method in which a fibrous sheet is impregnated and a resin is cured in a fibrous sheet under a dryer and, if necessary, a pressure condition, a fine powder or solution of the composition is applied to a substrate, Examples thereof include a coating method of curing the composition above and a method of molding such as a decorative board molding method of impregnating a printing paper or the like with the composition solution, drying and then heating and pressing the composition to cure the composition. The heating temperature for curing during molding may be, for example, a temperature of about 60 to about 220°C. Further, as the pressure when the pressurizing condition is adopted, a pressure such as about 5 to 1000 kg/cm ² can be exemplified. The composition of the present invention can be used as a molding material in a wide range of fields such as artificial marble by utilizing its good transparency.

[0023]

EXAMPLES The present invention will be described in more detail with reference to the following examples. Reference Example-1 (Synthesis of allyl ester oligomer) In an autoclave equipped with a reaction distillation apparatus, 5.0 kg of diallyl terephthalate monomer (DATP), 1.42 kg of propylene glycol (PG), dibutyltin oxide (D
(BO) (5.0 g) was charged, and after sufficiently substituting with nitrogen, the mixture was heated to 180° C. to distill off the produced allyl alcohol. When the distillation rate of allyl alcohol became slow, the reaction system was depressurized to increase the distillation rate of allyl alcohol. When 90% of the theoretical amount of allyl alcohol was distilled, the reaction temperature was set to 200° C. and the pressure of the reaction system was reduced to 0.1 mmHg by a vacuum pump to continue the reaction for 2 hours. The obtained product was extracted on a vat at 150° C., cooled to room temperature, and then ground to give a sample for evaluation.

Reference Examples-2 to 7 Allyl ester oligomers were synthesized in the same manner as in Reference Example-1, except that the starting materials were different. Table 1 shows the analytical values of the obtained allyl ester oligomer. In addition, about the analysis of the allyl ester oligomer in Table 1, it measured by the following method.

A) Method for determining iodine value The allyl ester oligomer is precisely weighed in the range of 0.30 to 1.0 g, put in a 200 ml iodine flask, and 30 ml of chloroform is added to completely dissolve the sample. to this,
Wijs reagent (7.9 g iodine trichloride and iodine 8.
2 g of each is dissolved in 200 to 300 ml of glacial acetic acid, and then both solutions are mixed to make 1 l), exactly 20 ml of which are added with a whole pipette, and then 10 ml of 2.5% mercuric glacial acetic acid glacial acetic acid solution is added. After that, leave it in the dark for 20 minutes to complete the reaction.

5 ml of newly prepared 20% KI solution
In addition, using 1% starch solution as an indicator, 0.1N-N
Titrate with a ₂ S ₂ O ₃ standard solution. At the same time, perform a blank test.

[0027]

[Equation 1]

B) Method for determining Mn and Mw by GPC method Mn and Mw in terms of polystyrene are measured by GPC. S
HODEX column AC-80P, 802, 804, 80
6 One by one is connected in series in this order, chloroform is used as a solvent, and measurement is performed at a temperature of 25° C. and a flow rate of 1.0 ml/min. First, at least 10 kinds of commercially available standard polystyrenes with known average molecular weights were used, and the retention time of each was determined together with the DATP monomer. A calibration curve was prepared by approximating the relationship between the average molecular weight and the retention time with a cubic curve or a polygonal line. 20 mg sample to 20 ml chloroform
Dissolve in 0.5 ml and inject 0.5 ml into the column through a line filter using a loop injector. The elution curve data obtained is automatically calculated in a data processor such as Shimadzu CR-3A based on the calibration curve created in M
Calculate n and Mw. Here, the peak was divided at intervals of 10 seconds, the molecular weight of each division point was Mi, and the height of the peak was Hi, and calculation was performed by the following formula.

[0029]

[Equation 2]

[0030]

[Table 1]

Examples 1 to 7 Unsaturated polyester resins at the compounding ratios shown in Table 2, allyl ester oligomers synthesized in Reference Example, and 2 phr of Perhexa C (a peroxide made by NOF CORPORATION) as an initiator were mixed to form a spacer. Insert it in a glass plate that has a silicone tube to prevent it from leaking, and in a gear open at 100°C for 2
Curing was performed at 140° C. for 2 hours. The cured products of Examples were all transparent, and the total light transmittance is shown in Table 2. Table 2 also shows the results of the volumetric shrinkage obtained from the specific gravity of the obtained cast cured product and the specific gravity before curing. From the results of Table 2, it can be seen that the volumetric shrinkage is lower than that of the resin of Comparative Example cured in the same manner as the Example shown in Table 3.

[0032]

[Table 2]

[0033]

[Table 3]

[0034]

INDUSTRIAL APPLICABILITY According to the present invention, an unsaturated polyester resin, which has a high shrinkage ratio and is easily cracked, is shrunk without impairing the transparency by the presence of an allyl ester oligomer having an allyl group at the end. The rate can be reduced. Particularly, it is effective for use in a field where transparency is required.

Claims (1)

(57) [Claims] 1. The degree of unsaturation expressed by iodine value measured by Wijs method is 2 to 45, and the polystyrene reduced number average molecular weight measured by GPC is 1000 to 50,000.
There is an allyl ester group at the terminal, the mole fraction of structure-A is in the range of 50 to 100%, the rest is structure-B, and 2 to 60% by weight of an allyl ester oligomer having the following repeating units, A polymerization composition in which the balance is an unsaturated polyester resin. -(CORCOOBO)- structure-A-(CORCOO) _x -ZO-CORCOO- structure-B [wherein R is an organic residue derived from a divalent carboxylic acid having 2 to 18 carbon atoms, B Is a divalent organic residue derived from a diol having 2 to 20 carbon atoms, and x is 2
It is an integer of not less than 6 and Z represents an organic residue derived from a polyol having 3 to 8 carbon atoms and having x+1 hydroxyl groups. ]