JPS6346256A - Unsaturated polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition usable for sheet molding compound, etc., having improved viscosity characteristics of compound before it is cured, improved surface characteristics, etc., by blending an unsaturated polyester with specific amounts of specified modified hydrogenated block copolymer and modified block copolymer. CONSTITUTION:(A) 10-90pts.wt. unsaturated polyester is blended with 2-70pts. wt. total amounts of (B) a modified hydrogenated block copolymer which is obtained by bonding a molecular unit containing a carboxylic acid (derivative) group to a hydrogenated block copolymer which is prepared by hydrogenating >=80% aliphatic double bonds based on conjugated diene in a block copolymer consisting of a polymer block A comprising one or more vinyl aromatic compounds as a main component and a polymer block B comprising one or more conjugated diene compounds as a main component and (C) a modified block copolymer obtained by bonding a molecular unit containing a carboxylic acid (derivative) group to the block copolymer, (D) 10-80pts.wt. vinyl monomer and further (E) 0.1-10pts.wt. based on 100pts.wt. total amounts of the components A-D of a curing agent.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to the viscosity characteristics of Con Guran P before curing, the surface characteristics (surface smoothness, surface gloss) of molded products after curing,
Endurance I! r11! The present invention relates to an unsaturated polyester resin composition that can be used as a sheet molding compound (sMo) or a sheet molding compound (BMO) that exhibits excellent properties.

(Conventional technology and its problems) In recent years, as the movement to reduce the weight of automobiles has become more active,
Attempts to use unsaturated polyester resins for exterior panel parts and structural parts of automobiles are becoming more popular.

Generally, molded products using unsaturated polyester resin are
Since the mold shrinkage rate during curing is as high as 4 to 12%, pristyrene, polymethyl methacrylate, and l
Thermostable resins such as polyvinyl acetate are blended as "low shrinkage agents."

However, even in this case, if the unsaturated polyester resin and the low-shrinkage agent undergo phase separation after Con-Grain P, undesirable surface characteristics such as warping and corrugation still occur even if the molded product is formed. The current situation is that

Therefore, in unsaturated polyester resin compositions, in addition to improving impact resistance, there is a tendency for emphasis to be placed on surface properties and thickening properties after condensation, and improvement thereof has become an important issue. There is. Therefore, many attempts to improve these improvements have been proposed.
No. 80 proposes a method of adding a styrene-butadiene block copolymer. However, in these methods, the added styrene-butadiene block copolymer component and unsaturated polyester resin component undergo phase separation after compounding/rounding, resulting in a cured product with poor surface properties and impact resistance. The reality is that it is not.

In an attempt to improve this drawback, Japanese Patent Application Laid-Open No. 52-1485
No. 88 and JP-A-54-130653 propose a method of adding a styrene-butadiene block copolymer containing a carboxyl group or a salt thereof at the end of the molecular chain. However, even with these methods, the problem of phase separation between the male component and the unsaturated ester component cannot be essentially solved, and the actual situation is that the surface properties and impact resistance have not been improved. Under these circumstances,
Furthermore, an attempt was made to improve this drawback in JP-A-56-11.
5309 and JP-A-56-115310, the content is that a modified block copolymer component in which a dicarzene acid group and/or its derivative group is bonded to a styrene-butadiene block copolymer is proposed. The amount added is expressed as a percentage. Also, for the same purpose, JP-A-58-8
No. 718 discloses that a modified block copolymer in which a molecular unit containing a carzene acid group or a derivative group thereof is bonded is added to a hydrogenated block copolymer obtained by hydrogenating a stene-butadiene block copolymer. A method is proposed. However, although the use of these modified block copolymers has improved the above-mentioned problem of phase separation after comparator with the unsaturated polyester component, the surface properties of the cured products obtained are still insufficient, and From a manufacturing perspective, we are concerned that the viscosity of the handle ring is too high or that its thickening properties are still insufficient.

(Means for Solving the Problems) The present invention has been made to solve the above-mentioned problems under the conventional technology, and by using specific components, surface smoothness, surface gloss, and dimensional stability can be improved. Excellent unsaturated ha?
It has been discovered that a cured composition of a polyester resin composition can be obtained, and it has also been discovered that the composition is a practically useful composition.

Therefore, the present invention provides (e) unsaturated 4! Reester resin (b) Hydrogenating a block copolymer consisting of a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block B mainly composed of at least one conjugated diene compound, At least 80% of the aliphatic double bonds based on conjugated diene compounds in the copolymer? A modified hydrogenated block copolymer in which a molecular unit containing a caldic acid group or a derivative group thereof is bonded to a hydrogenated block copolymer (c) A polymer mainly composed of at least one vinyl aromatic compound Modified block copolymer (d) in which a molecular unit containing a carzene acid group or its derivative group is bonded to a block copolymer consisting of block A and polymer block B mainly composed of at least one conjugated diene compound. Vinyl monomer (e) Hardening agent? To provide an unsaturated polyester resin composition characterized in that it is made by blending.

The present invention will be described in detail below.

The unsaturated polyester resin used as component (e) in the present invention is obtained by a condensation reaction of a mixture of α,β-unsaturated dibasic acid and a saturated dibasic acid with a polyhydric alcohol. be. Examples of the dibasic acid component include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, chlorinated maleic acid, glutaconic acid, and acid anhydrides thereof. In addition, examples of saturated dibasic acids include phthalic acid, halogenated phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hetacetic acid, endomethylenetetrahydrophthalic acid, succinic acid, a-cubic acid, glutaric acid, and hexanotine. Mention may be made of acids, pimelic acid or their acid anhydrides. Furthermore, if necessary, monobasic acids such as acrylic acid and methacrylic acid, and polybasic acids such as trimellitic acid, hemimellitic acid and trimesic acid can be used in combination with the above-mentioned dibasic acids as a modifying agent. Ethylene glycol is a polyhydric alcohol,
Diethylene glycol, triethylene glycol, polyethylene glycol, fluoropylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1.3J tanediol, tetramethylene glycol, 1.6-hexanediol, neopentyl glycol, 1.4 -Cyclohexane dimetatool, hydrogenated bisphenol A1, ethylene oxa-ide and/or propylene oxide adducts of bisphenols, etc. can be mentioned. Further, if necessary, higher aliphatic alcohols such as amyl alcohol, hexyl alcohol, pentyl alcohol, octyl alcohol, etc., monohydric alcohols such as tetrahydrofurfuryl alcohol, polyhydric alcohols such as glycerin, pentaerythritol, trimethylolethane, sorbitol, etc. It can also be used in combination with alcohol.

Next, the modified hydrogenated block copolymer used as component (b) of the present invention is a polymer block copolymer mainly composed of at least one vinyl aromatic compound and at least one conjugated diene compound. A block copolymer consisting of polymer block B is hydrogenated, and at least 8 of the aliphatic double bonds based on the conjugated diene compound in the copolymer are hydrogenated.
0% hydrogenated block copolymer with carzene acid group-! In particular, it is a modified block copolymer (hereinafter abbreviated as modified hydrogenated block copolymer) in which molecular units containing the derivative group are bonded.

Here, the hydrogenated block copolymer is, for example, A-B,
Person-B-A, B-A-B A, (A B
It is a hydrogenated vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as f4Sl or A-B-A-B-A.

This hydrogenated block copolymer contains 5 to 5 vinyl aromatic compounds.
Containing 60 weight f1%, preferably 10 to 40]i weight%, and further referring to the block structure, the polymer block 8 mainly composed of vinyl aromatic compounds is ``vinyl aromatic compound polymer block'' or ``vinyl aromatic compound polymer block''. Compound s
It has a structure of a copolymer block of a vinyl aromatic compound and a hydrogenated conjugated diene compound containing more than 70% by weight, preferably 70% by weight or more, and further,
Polymer block B mainly composed of a hydrogenated conjugated diene compound is a hydrogenated conjugated diene compound polymer block, or a hydrogenated conjugated diene compound polymer block containing 50% hydrogenated conjugated diene compound.
It has a structure of a copolymer block of a hydrogenated conjugated diene compound and a vinyl aromatic compound containing more than 70% by weight, preferably 70% by weight or more. In addition, polymer block A mainly composed of these vinyl aromatic compounds
, the polymer block B mainly consisting of a hydrogenated conjugated diene compound is a hydrogenated conjugated diene compound in the molecular chain of each polymer block! Itl'J: The distribution of vinyl aromatic compounds is random, Chibird (the monomer component increases or decreases along the molecular chain)
, partially block-like, or any combination thereof, each consisting of a polymer block mainly composed of a vinyl aromatic compound and water; If there are more than
Each block may have the same structure or may have different structures.

As the vinyl aromatic compound constituting the hydrogenated block copolymer, one or more kinds are selected from, for example, styrene, α-methylstyrene, hinyltoluene p75r, 3-phthylstyrene, etc., and styrene is preferred among them. Further, examples of the conjugated diene compound before hydrogenation constituting the hydrogenated conjugated diene compound include butadiene, isoprene, 1.3-pentadiene, 2.3-
One or more are selected from dimethyl-1,3-butadiene and the like, with sitadiene, isoprene and a combination thereof being preferred. The microstructure of the polymer block mainly composed of a conjugated diene compound before being hydrogenated can be arbitrarily selected. For example, in the case of a -liptadiene block, a 1,2-
Vinyl bond structure is 10-80%, preferably 25-65%
%.

The number average molecular weight of the hydrogenated pro- and tsuku monomer is 5, o
oo~1,000,000, preferably 10,000~
800.000.

More preferably, the range is from 30,000 to 300,000, and the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is 10 or less.

The molecular structure of the hydrogenated block copolymer provided in the present invention may be linear, branched, radial, or any combination thereof. It may be obtained by any method. For example, a vinyl aromatic compound-conjugated diene compound block copolymer is synthesized in an inert solvent using a lithium catalyst or the like according to the method described in Japanese Patent Publication No. 40-23798, and then, for example, It can be synthesized by hydrogenation in the presence of a hydrogenation catalyst in an inert solvent according to the methods described in Japanese Patent Application Laid-Open No. 8704-1987 and Japanese Patent Application Laid-open No. 133203-1983. In this case, at least 80% of the aliphatic double bonds based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer are hydrogenated, and the polymer block mainly composed of the conjugated diene compound is morphologically olefinic. The compound can be converted into polymer block B. In addition, regarding the hydrogenation rate of aromatic double bonds based on the vinyl aromatic compound copolymerized with the block person mainly consisting of a vinyl aromatic compound and, if necessary, the polymer block B mainly consisting of a conjugated diene compound. Although there is no particular restriction on hydrogenation, it is preferable that the hydrogenation rate be 20% or less. The amount of unhydrogenated aliphatic double bonds contained in the hydrogenated block copolymer can be measured using an infrared spectrophotometer,
This can be easily determined using a nuclear magnetic resonance apparatus or the like.

The modified hydrogenated block copolymer bonded with a molecular unit containing a carzene acid group or its derivative group used as component (b) is a hydrogenated block copolymer having the above-mentioned structure with α,β-unsaturation. Unsaturated caronic acids, their anhydrides, esters, etc. (hereinafter referred to as α).

A graft reaction is performed with a β-unsaturated carnoic acid (abbreviated as abbreviated as β-unsaturated carnoic acid) in the presence or absence of an organic peroxide, and the reaction may be carried out in either a dissolved state or a solution state. In addition, the modified hydrogenated block copolymer contains 0.05 to 10ii parts of α and β per 100 parts by weight of the hydrogenated block copolymer.
-The one to which unsaturated carbenoic acids are added is the ((
b) Can be used as a component. Addition amounts other than this will not give favorable results regarding the thickening properties and phase separation in the resulting unsaturated polyester resin composition. This is not preferable because it gives a much higher viscosity than the original viscosity and makes molding difficult. Therefore, outside of these additional amounts,
This is not preferable because it causes non-uniformity in surface characteristics and physical properties of the resulting cured product.

By the way, α and β that can be provided during the grafting reaction
- Examples of unsaturated carzenic acids include maleic L m
Hydromaleic acid, fumaric acid, itaconic acid, acrylic acid, acrylic ester, crotonic acid, cis-4-cyclohexene-1,2-dicarzenic acid and its anhydride, endo-cis-bicyclo(2,2,1 )-5-hebutene-2,
Examples include 3-dicarzonic acid and its anhydride, maleimide P, and among these, maleic anhydride is preferred.

In addition, examples of organic peroxides include dicumyl sooxane P1, dicumyl sooxane P1, and dicumyl sooxane P1.
art-butylcumylperoxyr, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and 2,5-dimethyl-2,5-di(tert-butyl g-oxy)hexane -3,n-butyl-4,4
-bis(tert-butylnooxy)nonolelate,
1.1-bis(tert-butylnoxy)3,3.
5-)limethylcyclohexane, etc., and can be suitably selected from these. The method for producing the modified hydrogenated block copolymer is not particularly limited in the present invention, but if the obtained modified hydrogenated block copolymer has a structure different from the above-mentioned characteristics, Production methods that contain undesirable components such as gel or that significantly increase the melt viscosity and deteriorate processability are not preferred. As an example of a preferred manufacturing method, for example, 150
Hydrogenated block copolymer, α, as described above at a temperature of ~350 °C
There is a method of melt-kneading β-, β-carboxylic acids, and organic peroxides to radically modify them. The obtained modified hydrogenated block copolymer may be ionomerized with a monovalent or higher valent metal ion.

Furthermore, in the modified hydrogenated block copolymer thus obtained, unreacted α, β-, β-carboxylic acid or its derivatives generally remain as unreacted substances; This unreacted material may be completely removed or may be left as is.

Next, the modified block copolymer used as component (c) of the present invention comprises a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block A mainly composed of at least one conjugated diene compound. A modified block copolymer in which a molecular unit containing a carboxylic acid group or its derivative group is bonded to a block copolymer consisting of a combined block B (
Hereinafter, it is abbreviated as a modified block copolymer).

Here, the block copolymer is, for example, A-89-
It is a male nyl aromatic compound-conjugated diene compound block copolymer having a structure such as B-person, B-person-B-A, (AB+T8i, person-B-A-B-person, etc.), and (b) Any block copolymer can be used as this block copolymer as long as it satisfies the above-mentioned requirements as a block copolymer before modification and hydrogenation of the modified hydrogenated block copolymer used as a component.However, If the polymer block mainly composed of a conjugated diene compound is, for example, a polymer block mainly composed of butadiene,
．． The 2-vinyl bond may be 70% or less.

The modified block copolymer bonded with molecular units containing a carzenic acid group or its derivative group used as component (c) is a block copolymer having the above-mentioned structure with an α,β-unsaturated caronic acid group. Its anhydrides, esters, etc. (hereinafter abbreviated as α, β-, β-calcenoic acids)
It is obtained by carrying out a graft reaction in a molten state or a solution state with or without the use of a radical initiator. The production method is not particularly limited in the present invention, but there are cases where the resulting modified block copolymer contains undesirable components such as gel, and its fluidity decreases, resulting in poor processability. This method is not preferred; for example, a method in which additives such as antioxidants are added in an extruder or the like and the modification reaction is carried out under melt-mixing conditions that substantially do not generate radicals is preferred.

The modified block copolymer that can be used as component (e) of the present invention has 0.05 to 1071 parts by weight of α,β-unsaturated carbenoic acids added to 100 parts by weight of the block copolymer. It is something that Addition amounts other than these do not give favorable results regarding the consistency of the resulting unsaturated/IJ ester resin composition, the thickening properties after e-landing, and the phase separation. During the preparation of the run P, a comparan P with a viscosity much higher than the desired viscosity at the time of molding is given, which is no longer preferable because it becomes difficult to mold. Therefore, addition amounts outside these ranges are not preferable because the resulting cured product will have non-uniformity in surface characteristics and physical properties.

Here, α9. As θ-unsaturated calzenic acids,
It can be arbitrarily selected from among the α,β-unsaturated carbenoic acids used in the graft modification reaction of the hydrogenated block copolymer mentioned above, and among these, maleic anhydride is preferred.

The obtained modified block copolymer may be ionomerized with a monovalent or higher valent metal ion, and further, unreacted α, β-unsaturated carbenoic acids remain in the modified block copolymer. It may be removed completely.

The vinyl monomer used as component (d) in the present invention acts as a crosslinking component. Examples of vinyl monomers include styrene, various substituted products of styrene, such as α-methylstyrene, vinyltoluene, dimethylstyrene, trimethylstyrene, halogenated styrene, tart-butylstyrene, styrene sulfonate, and aminostyrene. , P-benzystyrene, P-phenoxystyrene and other vinyl aromatic compounds, acrylic acid or methacrylic acid and methyl alcohol, ethyl alcohol, propyl alcohol,
Esters with aliphatic alcohols such as octyl alcohol, hexanol, tetrahydrofurfuryl alcohol, ethylene glycol, propylene glycol, etc., 2-
Aminoethyl-methacrylate, N,N-diethylamino-acrylate, N.

Acrylic acid or methacrylic acid derivatives such as N-quethylaminomethacrylate, α,β-unsaturated dicarzenic acids such as maleic acid, fumaric acid, crotonic acid, itaconic acid, etc., or their acid anhydrides, esters, amides, Fumaric acid esters such as diethyl- and dioctyl fumarate, as well as various vinyl monomers and vinylidene monomers, such as ImiP, such as acrylonitrile, methacrylaterile, vinyl acetate, vinyl chloride, vinylidene chloride, pinylene carsenate, vinyl-2- Chloroethyl ether, alkyl vinyl ether of 0INC18, vinyl ester of fatty acid of ○～C18, 2-vinyl 7ran, vinylphenol, vinylphenyldisiloxane, 2
-vinylpyridine, 4-vinylpyridine, vinylpyrrole, vinylpyrrolidone, vinylsulfonic acid, vinylurethane, methylvinylketone-2-vinylquinoline, vinylcarnolozole and the like. In addition, conjugated diene compounds such as 1,3-butadiene, isoprene, piperylene, methylpentadiene, and chloroprene;
Flucoxy and cyanide derivatives of conjugated dienes such as -methoxybutadiene and 1-cyanobutadiene can also be used. Additionally, polyfunctional crosslinkable vinyl monomers, such as sialyl evamaleate, diallyl phthalate, divinylbenzene, divinyl ether, neopentyl glycol diacrylate, diallyl cyanurate, triallyl cyanurate, diallylphenyl phosphatide), 2.3-
dipinyl 1,1,)n, dipinyl sulfone, 2.5
--) Vinyl-6-methyl 2-lysine and the like can also be used.

Preferred examples of these vinyl monomers include styrene, vinyltoluene, α-methylstyrene, chlorostyrene, divinylbenzene, methyl methacrylate, methyl acrylate, diallyl phthalate, and triallyl cyanurate.

As the curing agent as component (c) used in the present invention, organic peroxy-P, organic hydro, 6-oxy-r, and azo compounds can be used.

Some -g-oxides useful in the present invention include dialkyl peroxide P and diacyl peroxide P.

Alkyl peroxides have the general structure R-00-R', where R and R' are the same or different.
A secondary or tertiary alkyl group, a cycloalkyl group, an aralkyl group or a heterocyclic group. The groups of peroxides suitable for use in the present invention include dicumyl oxide, dicumyl oxide, di-tart-butyl oxide,
tert-butylcumyl peroxy P and 2.5-
Dimethyl-2,5-bis(tert-butylperoxy)hexane is included.

Diacylnomycelain oxide has a general structure (concavity) Ooc (o
) u', in which case R and R' are the same or A
These are alkyl groups, cycloalkyl groups, aralkyl groups, aryl groups or heterocyclic groups. Some examples of diacyl oxides suitable for use in the present invention include dilauroyl oxide, dipenzoyl oxide, dicetyl peroxide P1 sidecanoyl oxide, di(2,4-dichlorobenzoyl) Peroxides include diisononanoyl peroxide P and 2-methylpentanoyl peroxide. In addition, other oxidized oxides useful in the present invention include particularly preferred peresters, such as tert-butyl peroctoate and tert-butyl noonzoate, as well as 1 methyl ethyl ketone oxidized cyclohexanone oxide. etc. are included.

Examples of hydroperoxides suitable for use in the present invention include tert-butylhyPlonooxide, cumylhyPlonozo-oxai)', 2,5-dimethyl-2,5--, ffhyPlonozo oxyhexane,
There are P-methane-hydro-oxy-P and diisopropylbenzene-hydro-peroxide.

Examples of azo compounds that can be used in the present invention include diazoamino-4-benzene, N,N'-dichloroazodicarzenic acid amide P
1-Azodicarzenic acid diethyl ester, 1-cyano-1
-(tart-butylazo)cyclohexanone and azobis(imbutyronitrile).

The blending ratio of each component constituting the composition of the present invention is (a)
~ (d) For m 11100 M 21 parts of component, (
e) Component #-tlO ~90 parts by weight, preferably 20-8
0 parts by weight, preferably 20 to 60 parts by weight,
The total amount of component (f) and component (c) is 2 to 70 parts by weight, preferably 5 to 50 parts by weight, more preferably 5 to 4 parts by weight.
Total weight is 0, and component (b)/component (c) = 0.1
It is necessary to satisfy the conditions of 1 to 9 ('Mfi ratio). If this ratio is 0.11, the initial viscosity of Comparan P will be low, the fluidity during heating will be high, and the glass fibers will not be uniformly dispersed, making it impossible to obtain a homogeneous molded product. On the other hand, if the ratio (force) exceeds 9, the initial viscosity of the condenser run P will be too high, resulting in excessive shear at the time of crosstalk, undesirable cutting of glass fibers, or fillers and coatings. Since the surface temperature of the glass rain during the impregnation process is insufficient, a molded product with improved surface properties cannot be obtained. Therefore, it is necessary to keep the ratio within the above range, and as a result,
The viscosity of Connoise P is 40 to 6 in BMO.
A cured product of an unsaturated polyester resin composition that has excellent surface smoothness, surface gloss, dimensional stability, and impact resistance when molded at around 00,000 poise, or around 100,000 to 300,000 poise in SMO. bring.

Next, component (d) is in the range of 10 to 80 parts by weight, preferably 2 to 70 parts by weight.

Further, the amount of the curing agent used in the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, based on a total of 100 parts by weight of components (1) to (d). is 0.5~
It is 3 parts by weight.

The composition of the present invention may contain other additives as necessary, such as thickeners, fiber reinforcing agents, inorganic brightening agents, low shrinkage agents,
Pigments, colorants, lubricants, mold release agents, etc. can be added. The thickeners used in this initiative are oxides and/or hydroxides of metals from group Ⅰ of the periodic table, such as magnesium,
Selected from oxides and hydroxides of calcium, strontium, nitrate and zinc. Preferred are magnesium and/or calcium oxides or hydroxides.

The above-mentioned thickener is 0.5 to 10 parts by weight, preferably 1 part by weight, per 100 parts by weight of the total of components (e), (b), (c), and (d) of the composition of the present invention. used in an amount of ~5 parts by weight.

The fiber reinforcement used in the present invention is selected from fibers such as glass, silicate, asbestos, cellulose, carbon, graphite, polyester, polyacrylic, polyamide, and polyolefin. Preferred is glass fiber.

The above-mentioned fiber reinforcing agent comprises component (e) of the composition of the present invention, component (b)
It is used in an amount of 5 to 300 parts by weight, preferably 20 to 200 parts by weight, and more preferably 20 to 100 parts by weight, based on 10 parts by weight of components (), (c), and (d).

The filler used in the present invention is preferably an inorganic particulate optical filler, such as calcium carbonate, calcium silicate, silica, calcined clay, chalk, melk, limestone, anhydrous calcium sulfate, norium sulfate, asbestos, powdered glass, quartz. , aluminum hydrate, aluminum oxide, antimony oxide, etc.

The above-mentioned photosensitizers are (a) component of the composition of the present invention, (b)
component, (c) component, cd) component, 50 to 800 loo if part, preferably 100 to 400
It is used in an amount of 200 to 300 parts by weight, more preferably 200 to 300 parts by weight.

Low shrinkage agents that can be used in the present invention include polystyrene-based, poly(meth)acrylate-based, polyvinyl acetate-based,
It is selected from homopolymers or colimers such as polyvinyl chloride-based, polyethylene-based, polypropylene-based, Iriamyr-based, 4-licasenate-based, and cellulose-based polymers. Main copolymers include homolymers of methyl methacrylate, ethyl methacrylate, butyl methacrylate and ethyl acrylate, and copolymers of methyl methacrylate with acrylic acid and methacrylic acid and/or their lower alkyl esters. For example, methyl methacrylate containing a small amount of one or more of lauroyl methacrylate, isozenyl methacrylate, acrylamide, hydroxyethyl methacrylate, styrene, 2-ethylhexyl acrylate, acrylonitrile, methacrylic acid, methacrylamide, and methyloylacrylamide P1 cetylstearyl methacrylate. Examples include copolymers.

Other useful copolymers include styrene-acrylonitrile, vinyl chloride-vinyl acetate, and the like.

These low shrinkage agents are the (-) component of the composition of the present invention, C
It is used in an amount ranging from 0 to 40 parts by weight, preferably from 2 to 20 parts by weight, based on a total of 100 parts by weight of component b), component (c) and component (d).

In addition to the above, the composition of the present invention includes, for example, pigments, colorants, lubricants or mold release agents, stabilizers, silane coupling agents,
Flame retardants and the like can also be added. Specific examples of pigments include titanium oxide, casen black, and phthalocyanine.

Examples of lubricants or mold release agents include aluminum, calcium, magnesium, and zinc salts of stearic acid.

Stabilizers include alkylphenols, quinones, amines, tin octoate, tris(nonylphenyl)phosphite, BHT, etc.

A preferred method for producing the unsaturated/lyester resin composition of the present invention is as follows.

In other words, a first mixture containing an unsaturated ester resin as the component (e) of the present invention and a vinyl monomer as the component (d), and a modified hydrogenated block copolymer as the component (b). and a second mixture containing the modified block copolymer as the component (c) and a vinyl monomer as the component (d); This is a manufacturing method in which a curing agent is mixed with additives such as a filler, a fiber reinforcing agent, a thickener, a low shrinkage agent, and a mold release agent as necessary. In particular, it is preferable to mix the filler into the second mixture. This method is a preferred method for suppressing phase separation between the modified hydrogenated block copolymer and the modified block copolymer and the unsaturated polyester resin.

The unsaturated polyester resin composition of the present invention described above is
Preferably, it can be formed into a cured product by passing through an intermediate comparan P such as 8MO or BMO, and then molding by a method such as compression molding or injection molding.

(Effects of the Invention) The present invention improves the initial viscosity of the concrete by setting the component (b) and the component (c) at a specific blending ratio, and reduces the decrease in viscosity during heating, and the surface It is possible to provide an unsaturated polyester resin composition with excellent properties, dimensional stability, and impact resistance, and its fields of use include automobile parts, transportation equipment such as boats, construction equipment such as bathtubs and septic tanks, chairs, etc. and other industrial products.

(Examples) In order to explain the present invention in more detail, the present invention will be explained using examples, but the present invention is not limited to these examples.

(1) Preparation of unsaturated polyester resin as component (e) 0.7 mol of maleic anhydride, 1.4 mol of phthalic anhydride,
A mixture consisting of 2.0 mol of fluoropylene gellicol and 0.2 mol of diethylene glycol was heated at about 100°C under a nitrogen stream.
The temperature was raised to about 210° C. while stirring and condensed water was removed from the system, and an esterification reaction was carried out at this temperature to synthesize an unsaturated polyester resin with an oxidation level of 40. This unsaturated polyester resin is dissolved in styrene,
Solid content concentration 651! % solution was used as component (a-1).

Furthermore, 0.6 mol of isophthalic acid, 0.6 mol of 7-talic anhydride
A mixture consisting of 1.4 moles of m-water maleic acid and 2.6 moles of propylene dalicol was subjected to an esterification reaction in the same manner as described above to synthesize an unsaturated ester resin with an oxidation level of 30. This unsaturated polyester resin was dissolved in styrene, and a solution with a solid content concentration of 65'M was prepared as (a-2).
as an ingredient.

(2) Synthesis of modified hydrogenated block copolymer of component (b) It has the structure of hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene-polystyrene, and the amount of bound styrene is 18% by mass, and the The amount of 1,2-vinyl bond in the 2-liptadiene moiety is 40%, and the number average molecular weight is 56.
,000, a molecular weight distribution of 1.04, and a hydrogenation rate of 98%, a hydrogenated block copolymer was synthesized using a Ti-based hydrogenation catalyst described in JP-A-59-133203. 100 parts by weight of this hydrogenated block copolymer, 1 part by weight of maleic anhydride, 2
,5-dimethyl-2,5-cy(tert-butylperoxy)
0.1 fi part by weight was mixed in hexane 1, and a modification reaction was carried out in a 501-diameter twin-screw extruder set at 250°C. The obtained modified hydrogenated block copolymer contains 0 maleic anhydride.
．． 75 parts by weight was added. This product was dissolved in styrene, and a solution with a solid content concentration of 30% by weight was used as component (b-1).

Next, it has a structure of (polystyrene-hydrogenated 9-polybutadiene-)7-st, the bonded styrene ft is 30% by weight, the amount of 1,2-vinyl bond in the polybutadiene part before hydrogenation is 60%, and the number average molecular weight is 93. ,000, a molecular weight distribution of 1.48, and a hydrogenation rate of 97%, a hydrogenated block copolymer was synthesized using a Ti-based hydrogenation catalyst described in JP-A-59-133203. Per 100 parts by weight of this hydrogen block copolymer, 0.5 parts by weight of maleic anhydride, 42001 parts by weight of dicumyl peroxa, and 0.2 parts by weight of magnesium hydroxide were mixed, and the mixture was heated to 230°C using a 40-diameter single-screw extrusion bar. The denaturation reaction was carried out under the following temperature conditions. The obtained modified hydrogenated block copolymer had 0.16 parts by weight of maleic anhydride added thereto. This material was dissolved in styrene, and the solid content was 30% by weight.
The solution was used as component (b-2).

Sara K1. T? Listyrene - Hydrogenated? Has a liptadiene-polystyrene structure, with a bonded styrene content of 30
%, the amount of 1,2-vinyl bonds in the polybutadiene moiety before hydrogenation is 32%, and the number average molecular weight is 44. OOO molecular weight distribution 1
．． 05, a hydrogenated block copolymer with a hydrogenation rate of 99% was synthesized using a hydrogenation catalyst described in JP-A-59-133203. This hydrogenated block copolymer Zo.

Per part by weight, 3.0 parts by weight of maleic anhydride, n-butyl 4.4-bis(tertiary butyloxy)
Mix 0.3 parts by weight and use a 30 mm diameter twin screw extruder to
The modification reaction was carried out under a temperature condition of 0°C. The obtained modified hydrogenated block copolymer had 2.1 parts by weight of maleic anhydride added thereto. This product was dissolved in styrene, and a solution with a solid content concentration of 30% by weight was used as component (ba).

(3) Synthesis of modified block copolymer of component (c) (
-Restyrene-2liptadiene→, has a structure of 81,
Bonded styrene filBiffi%, 1.2-vinyl bond amount in polybutadiene part is 42%, number average molecular weight 75.0
A block copolymer having a molecular weight distribution of 0.00 and a molecular weight distribution of 1.34 was synthesized. 100 parts by weight of this block polymer A6, 1 part by weight of maleic anhydride, and 1.5 parts by weight of stabilizer were mixed and heated to 240°C.
The modification reaction was carried out in a twin-screw extruder with a diameter of 50 mm. The resulting modified block copolymer had 0.03 parts by weight of maleic anhydride added thereto. Dissolve this in a styrene solution, and make a solution with a solid content concentration of 30fi% (c-1)
as an ingredient.

Next, it has a structure of 1 polystyrene-polybutadiene-polystyrene, with 40% by weight of bound styrene, 36% of 1,2-vinyl bonds in the polybutadiene part, and a number average molecular weight of 6.
9,000. A block copolymer with a molecular weight distribution of 1.05 was synthesized. 2 parts by weight of maleic anhydride and 1.5 parts by weight of a stabilizer are mixed per 100 parts by weight of this block copolymer,
The modification reaction was carried out in a twin screw extruder with a diameter of 30 nm set at 260°C. The obtained modified block copolymer had 0.4 parts by weight of maleic anhydride added thereto. This product was dissolved in a styrene solution, and a solution with a solid content concentration of 30% by weight was prepared (c
-2) component.

Furthermore, it has the structural components of polybutadiene-polystyrene, lIJ butadiene-polystyrene, the amount of bonded styrene is 20% by weight, the 1,2-vinyl bond in the polybutadiene portion is 12%, and the number average molecular weight is 83,000. Molecular weight distribution 1.0
A block copolymer of No. 4 was synthesized. 100 parts by weight of this block copolymer, 3 parts by weight of maleic anhydride, and 1.5 parts by weight of a stabilizer were mixed, and a modification reaction was carried out in a twin screw extruder of 50W+ diameter set at 250°C. The obtained psychopathic block copolymer had 0.7 parts by weight of maleic anhydride added thereto. This product was dissolved in a styrene solution to obtain a solution (c-3) component with a solid content concentration of 30]1i mass %.

(4) Component (d) is styrene in which the above-mentioned components (e) to (c) are dissolved.

(5) Tert-butyloxybenzoate was used as component (e).

Examples 1 to 4, Comparative Examples 1 to 2 Styrene solution of unsaturated polyester resin (a), styrene solution of modified hydrogenated block copolymer (with), styrene solution of block copolymer (c), tert- Blue A
-Oxybenzoate (e), zinc stearate, calcium carbonate, and magnesium oxide were blended according to the formulation shown in Table 1 to obtain Conomilan r before curing.

This Comparan P was aged in an oven at 40°C for 48 hours, and the viscosity of Comparan P at 23°C after aging and the viscosity of this aged Comparan A round at 70°C were measured using a Pruckviel P viscometer HBT type. Just in case. The results are listed in Table 1.

From these results, it was revealed that the unsaturated polyester resin composition of the present invention had a higher viscosity at 70° C. than the comparative example, and was characterized by less decrease in viscosity upon heating.

In the following margin Examples 5 to 8, Comparative Examples 3 to 4 Each of the basic formulations of Examples 1 to 4 and Comparative Examples 1 to 2 contained 1 glass fiber (PPG-3198; manufactured by PPG Corporation).
00 parts to prepare SMO, which was aged at 40°C for 48 hours. Thereafter, it was pressure-molded under the conditions of 140° C. and 85K17cm'' to obtain a cured unsaturated polyester resin composition. Table 2 shows the results of measuring the physical properties of each molded product.

From this result, the unsaturated polyester resin composition of the present invention has no surface smoothness such as "large undulations" or "small undulations", and has a smooth surface gloss of 60% or more, and has an excellent surface. The characteristics were shown. It was also found that the shrinkage rate during molding was negative (expansion), and that it had excellent effects as a low shrinkage rate. On the other hand, it has become clear that unsaturated polyester resin compositions other than those of the present invention are inferior in surface smoothness, surface gloss, and low shrinkage properties.

Margin below

Claims (1)

[Claims] (1) (a) Unsaturated polyester resin (b) A block consisting of a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block B mainly composed of at least one conjugated diene compound A hydrogenated block copolymer obtained by hydrogenating a copolymer to hydrogenate at least 80% of the aliphatic double bonds based on a conjugated diene compound in the copolymer contains a carboxylic acid group or a derivative group thereof. Modified hydrogen block copolymer with bonded molecular units (c) consisting of a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block B mainly composed of at least one conjugated diene compound An unsaturated polyester comprising: a modified block copolymer in which a molecular unit containing a carboxylic acid group or a derivative group thereof is bonded to a block copolymer; (d) a vinyl monomer; and (e) a curing agent. resin composition