JP2969826B2 - Thermoplastic resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a hydrogenated polymer composition having excellent mold release performance and excellent heat resistance and antistatic properties.

[Prior art] A resin having excellent thermal stability obtained by hydrogenating a polymer obtained by ring-opening polymerization of a norbornene derivative with a metathesis catalyst is:
This is disclosed in JP-A-01-240517 and the like.

[Problems to be Solved by the Invention] A ring-opened polymer of a norbornene derivative and a hydrogenated product thereof are used as a material for a lens, an optical information disc substrate, etc. by utilizing its excellent properties such as transparency, heat resistance and dimensional stability. The use of is expected.

Among optical molded products, especially optical disks and lenses are manufactured by injection molding, but when releasing from the mold,
If the release resistance is large, it causes warpage of the molded product and optical distortion. Furthermore, when the mold release resistance is large, a part of the surface of the molded article adheres to the mold surface, and the surface is separated. Therefore, it is necessary to use a release agent.

Conventionally, as a release agent for thermoplastic resin, metal soap,
Fatty acids, higher alcohols, fatty acid esters, bisamides, monoamides, fats and oils, silicone oils and the like are known. Among these, those having excellent release properties when used in a small amount are known to be metal soaps and fatty acid esters. However, when molded at a high temperature, such as a ring-opened polymer of a norbornene derivative, these release agents undergo thermal decomposition and lose their release effect. In addition, low molecular components generated by thermal decomposition may cause silver streaks and may have an adverse effect, and a sufficient release effect can be obtained by using a conventionally known release agent as it is. Can not.

Ring-opening (co) polymers of such norbornene derivatives,
In addition, various release agents have been studied in order to obtain releasability of the hydrogenated product during high-temperature molding. However, simply adding a commonly used metal soap-based or fatty acid ester-based release agent to the above-described polymer at the end still has insufficient release properties at the time of injection molding, and the effect of the addition is sufficiently observed. It was not possible at the moment.

Especially ring-opening (co) of norbornene derivatives having polar groups
Since the polymer is excellent in heat resistance, the molding temperature is high, and improvement of the releasability and the like is desired.

[Means for Solving the Problems] In view of such circumstances, the present inventors have conducted intensive studies for the purpose of obtaining a resin composition having excellent transparency, heat resistance, and excellent mold release properties. As a result, in producing a hydrogenated product of a ring-opened polymer of a norbornene derivative, a non-aromatic double bond present in the polymer was converted to a high hydrogenation rate far exceeding conventionally thought levels, that is, 60 MHz proton NMR. Addition of a specific aliphatic sulfonic acid metal soap-based mold release agent to hydrogenated and 95% or more is very effective, and the polymer has sufficient transparency, heat resistance and mold release. The present invention has been found, and the present invention has been achieved.

That is, the present invention relates to (a) opening of at least one kind of ring-opening polymer of a norbornene derivative represented by the following general formula (1) or at least one kind of the norbornene derivative and an unsaturated cyclic compound copolymerizable therewith. The copolymer obtained by performing the ring copolymerization is converted to the non-aromatic carbon present in the (co) polymer.
(B) 0.01 to 15 parts by weight of a metal salt of an aliphatic sulfonic acid having 10 or more carbon atoms in 100 parts by weight of a hydrogenated norbornene resin obtained by hydrogenating 95% or more of carbon double bonds. It is intended to provide a thermoplastic resin composition characterized in that:

Hereinafter, the present invention will be described in detail.

(Regarding hydrogenated norbornene-based resin (a)) The hydrogenated norbornene-based resin (a) in the present invention comprises:
Ring-opening (co) polymerizing at least one compound represented by the following general formula (I) alone or with another copolymerizable monomer in the presence of a metathesis catalyst, the obtained (co) polymer is obtained. It can be produced by subjecting to a hydrogenation reaction in the presence of a hydrogenation catalyst to hydrogenate 90% or more of the non-aromatic double bonds present in the molecule.

General formula (I) [In the formula, A and B represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X and Y represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, and a carbon atom substituted with a halogen atom. 10 hydrocarbon _{group, - (CH 2) n COOR} 1, - (CH 2) n O
COR ¹ ,-(CH ₂ ) _n CN,-(CH ₂ ) _n CONR ² R ³ ,-(CH ₂ ) _n C
_{OOZ, - (CH 2) n} OCOZ, - (CH 2) n OZ, - (CH 2) composed of _n W or X and Y, Wherein at least one of X and Y is a group other than a group selected from a hydrogen atom and a hydrocarbon group,
m is 0 or 1. Note that R ¹ , R ² , R ³ and R ⁴ are a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrocarbon group or a hydrocarbon group substituted with halogen, W is SiR ⁵ _p D _3-p (R ⁵ is a hydrocarbon group having 1 to 10 carbon atoms, D is an integer of halogen atom, -OCOR ⁵ or -OR ^5, p is 0 to 3), n is an integer of 0. In order to enhance the heat resistance of the final resin composition, at least one of the substituents X and Y in 100 parts by weight of the compound represented by the general formula (I) used for the production of the ring-opened polymer is required.
One preferably contains a compound other than a group selected from a hydrogen atom and a hydrocarbon group in an amount of 5 parts by weight or more, more preferably 10 parts by weight or more.
Further, one of the substituents X and Y has the formula — (CH ₂ ) _n COOR ¹
It is preferable that the carboxylic acid ester group represented by the formula (1) does not change in the hydrogenation step during resin production. Moreover, the formula - (CH ²⁾ Of the carboxylic acid ester group represented by _n COOR ^1, preferably since the heat resistance of the smaller ones as the final resin composition of n is high, in particular formula - the (CH _{2) n} COOR ¹ In the synthesis of a monomer that n = 0,
It is also preferable in view of the stability of the final resin composition. R ₁
Is an aliphatic, alicyclic, or aromatic hydrocarbon group having 1 to 20 carbon atoms.The higher the carbon number, the lower the water absorption of the obtained polymer is. As the number of carbon atoms increases, the carbon number increases.To maximize the characteristics of the present composition, a chain hydrocarbon group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 or more carbon atoms, or a phenyl group, A substituted phenyl group is preferred, and 8-methyl-
8 methoxycarbonyltetracyclo [4.4.0.1 ^{2, 5} .1
^7,10 ] -3-dodecene is particularly preferred.

The ring-opened polymer may be a copolymer using two or more compounds represented by the general formula (I). For example, 8
-Methyl-8-methoxycarbonyltetracyclo [4.4.
0.1 ^2,5 .1 ^7,10] -3-dodecene and 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] -2-heptene may be copolymerized. This combination of 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] -2-heptene is 8-methyl-3-methoxycarbonyl-tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] -3-dodecene It is particularly preferable because it can be obtained as an intermediate for production.

Further, as a compound represented by the general formula (I), 8-
Methyl-8-methoxycarbonyltetracyclo [4.4.0.
Represented by 1 ^2,5 .1 ^7,10] -3-dodecene and / or 5-methyl-5-and-methoxycarbonyl bicyclo [2.2.1] -2-heptene, no polar substituent general formula (I) Compounds such as bicycloheptene, tricyclodecene, tetracyclododecene, ethylidene norbornene,
2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,
A copolymer using a combination of 8a-octahydronaphthalene and the like is also preferable in that a polymer having high heat resistance and low water absorption is obtained.

Other monomers copolymerized with the compound (I) include cycloalkanes such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and dicyclopentadiene, and alkyl-substituted products thereof. Among these copolymerizable monomers, particularly preferred is dicyclopentadiene, which is easily available.

When a copolymer with the compound represented by the general formula (I) is obtained using a copolymerizable monomer, if the compound represented by the general formula (I) is small, the final resin composition has high heat resistance. Therefore, the proportion of the monomer of the general formula (I) is at least 10 mol%, preferably at least 30%, more preferably
It needs to be at least 50%.

Further, the polymerization of the compound represented by the general formula (I) is carried out by adding carbon-carbon double to the main chain of polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-propylene-non-conjugated diene copolymer, polynorbornene and the like. The reaction can be carried out in the presence of an unsaturated hydrocarbon-based polymer containing a bond. In this case, the final resin composition using the obtained polymer has particularly high impact resistance. Of these unsaturated hydrocarbon polymers, a butadiene-styrene copolymer and an isoprene-styrene copolymer are preferred because a transparent resin composition is easily obtained. In this case, the copolymer of diene and styrene may be a random copolymer or a block copolymer. Upon polymerization in the presence of an unsaturated hydrocarbon polymer, the polymer is 1 to 50% by weight, preferably 3 to 40% by weight, more preferably 5 to 30% by weight based on the compound represented by the general formula (I). used.

The metathesis polymerization used for ring-opening polymerization includes (A) W,
At least one compound selected from the group consisting of Mo and Re; and (B) at least one compound selected from the group consisting of elements of Group IA, IIA, IIB, IIIB, IVA and IVB.
The catalyst comprises at least one combination selected from those having a carbon bond or the element-hydrogen bond, but may be a catalyst to which an additive (C) for enhancing the catalytic activity is added.

Representative examples of W, Mo or Re compounds suitable as the component (A) include WCl ₆ , MoCl ₅ and ReOCl ₃ .

Specific examples of the component (B) include n-BuLi, (C _{2
H 5) 4 Al, (C} 2 H 5) 2 AlCl, and the like LiH.

As typical examples of the component (C), alcohols, aldehydes, ketones, amines and the like can be suitably used.

As for the use ratio of the component (A) and the component (B), (A) :( B) is used in a metal atom ratio of 1: 1 to 1:20, preferably 1: 2 to 1:10.

The working ratio of the component (C) to the component (A) is (C) :( A) in a molar ratio of 0.005 to 1 to 10: 1, preferably 0.05: 1.
Used in the range of ~ 2: 1.

The molecular weight of the polymer can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent. More preferably, α-olefins such as 1-butene, 1-pentene, 1-hexene, and 1-octene are used in the reaction system. It is advisable to adjust the amount by changing the amount.

The hydrogenation reaction of the (co) polymer obtained by the above metathesis ring-opening polymerization is carried out by a usual method. As the catalyst used in this hydrogenation reaction, those used in ordinary hydrogenation reactions of olefinic compounds can be used.

For example, examples of the heterogeneous catalyst include a solid catalyst in which a catalytic substance such as palladium, platinum, ruthenium, rhodium, and nickel is supported on a carrier such as carbon, silica, alumina, and titania. In particular, a catalyst in which palladium is supported on a silica / magnesia carrier is preferred from the viewpoints of activity, life, and the like.

Further, as a homogeneous catalyst, nickel naphthenate, titanocene dichloride, organic solvent-soluble nickel such as cobalt acetylacetonate, cobalt, titanium, vanadium compound and triethylaluminum, triisobutylaluminum, organic aluminum such as diethylaluminum monochloride, Alternatively, a catalyst in combination with an organic lithium such as butyl lithium can be used. Also, a noble metal complex catalyst such as chlorotris (triphenylphosphine) rhodium can be used.

The hydrogenation reaction is carried out under a hydrogen gas atmosphere at normal pressure to 300 atm, preferably 3 to 150 atm, at a temperature of 0 to 200 ° C, preferably 20 to 1 atm.
It can be performed at 80 ° C. The hydrogenation rate is measured by 60 MHz NMR, and is 95% or more, more preferably 98% or more, calculated from the decrease in the peak in the range of δ = 4.5 to 6.0 ppm due to the hydrogenation reaction.
It is particularly preferably at least 99%. If the degree of hydrogenation is less than 90%, a problem may occur in the stability of the resin composition, which is not preferable.

The component (b) used in the present invention is a metal salt of an aliphatic sulfonic acid having 10 or more carbon atoms.

As the metal salt of the aliphatic sulfonic acid having 10 or more carbon atoms, an alkali metal salt is preferable, and specific examples thereof include sodium 1-decanesulfonate, sodium 1-undecanesulfonate, sodium 1-dodecanesulfonate, Sodium 1-tridecanesulfonate, sodium 1-tetradecanesulfonate, sodium 1-pentadecanesulfonate, sodium 1-hexadecanesulfonate, sodium 1-heptadecanesulfonate, sodium 1-octadecanesulfonate, 1-nonadecanesulfonic acid Sodium, 1-eicosandecasulfonic acid sodium, 1-decanesulfonic acid potassium, 1-undecanesulfonic acid potassium, 1-dodecanesulfonic acid potassium, 1-tridecanesulfonic acid potassium, 1-tetradecanesulfonic acid potassium , Potassium 1-pentadecane sulfonic acid, potassium 1-hexadecane sulfonic acid, 1-
Potassium heptadecanesulfonate, potassium 1-octadecanesulfonate, potassium 1-nonadecanesulfonate, potassium 1-eicosandecasulfonate, lithium 1-decanesulfonate, lithium 1-undecanesulfonate, lithium 1-dodecanesulfonate Lithium 1-tridecanesulfonate, lithium 1-tetradecanesulfonate, lithium 1-pentadecanesulfonate, lithium 1-hexadecanesulfonate, lithium 1-heptadecanesulfonate, lithium 1-octadecanesulfonate, 1-nonadecanesulfone Lithium acid, lithium 1-eicosanedecasulfonic acid and isomers thereof can be mentioned.

The amount of the component (b) is based on 100 parts by weight of the component (a).
It is 0.01 to 15 parts by weight, preferably 0.05 to 7 parts by weight, more preferably 0.1 to 3 parts by weight, particularly preferably 0.2 to 2 parts by weight.

When the amount of the metal salt of the aliphatic sulfonic acid is less than 0.01 part by weight, the release resistance is hardly reduced. Also,
If the addition amount exceeds 15 parts by weight, the slip between the screw and the resin during plasticization becomes too large, resulting in measurement instability.
For this reason, silver is generated by air entrainment, and a sufficient effect cannot be exhibited.

When the thermoplastic resin composition of the present invention is used, the composition can be further stabilized by adding a known antioxidant or an ultraviolet absorber. In addition, additives used in conventional resin processing, such as a lubricant, can be added to improve processability. Further, it can be used by mixing with various other polymers for the purpose of improving impact resistance, chemical resistance, and abrasion resistance.
Polymers that can be mixed include those described in Japanese Patent Application No. 02-78844.

Polymer composition of the present invention, various known molding processing methods,
That is, a molded article can be obtained by applying an injection molding method, a compression molding method, an extrusion molding method, or the like.

[Examples] Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist.

In the following examples, various physical properties were measured under the following conditions.

Injection moldability: After pelletizing the polymer with a 30mmφ extruder at a temperature of 220 to 280 ° C, a plate of W = 80mm, L = 50mm, t = 2.4mm is manufactured by Niigata Iron and Steel Co., Ltd., NN30B type injection molding machine. Continuous molding was performed at a temperature of 300 ° C. and a cycle time of 30 seconds. The obtained plate was visually inspected to confirm the occurrence of silver and the presence or absence of peeling. A sample with silver was evaluated as x, and a sample without silver was evaluated as ○. Similarly, those with peeling were rated as x, and those without peeling were rated as o. In addition, the ejection pressure of the ejector when removing the molded product is measured by a pressure sensor (6157A
(Type).

The haze value of this molded product was measured by a multi-light source colorimeter manufactured by Suga Test Instruments Co., Ltd. based on ASTM D1003 for 5 molded products every 10 shots from the 20th shot. The lower the haze value, the better the transparency.

Reference Example 1 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene (hereinafter referred to as Compound 1) and 5 kg, 1,2-dimethoxyethane 3 kg, 12 kg of cyclohexane, 1250 g of 1-hexene, 170 ml of a 0.96 mol / toluene solution of diethylaluminum chloride in 50 ml
Was added to the pressure vessel. On the other hand, a 0.05 mol / l solution of tungsten hexachloride in 1,2-dimethoxyethane 1 was added to another flask.
And 500 ml of a 0.1 mol / l, 2-dimethoxyethane solution of paraaldehyde were mixed. 245 ml of this mixed solution was added to the mixture in the pressure vessel. After sealing, the mixture was heated to 80 ° C. and stirred for 3 hours. In the obtained polymer solution, 1,
2/8 of 2-dimethoxyethane and cyclohexane (weight ratio)
1/10 (weight ratio) by adding a mixed solvent of
Then, 1 kg of triethanolamine was added, and the mixture was stirred for 10 minutes.

25 kg of methanol was added to the polymerization solution, stirred for 30 minutes and allowed to stand. The upper layer separated into two layers was removed, methanol was added again, and the mixture was stirred and allowed to stand, and then the upper layer was removed. The same operation was performed twice more, and the lower layer obtained was cyclohexane, 1,2-
The solution was appropriately diluted with dimethoxyethane to obtain a cyclohexane / 1,2-dimethoxyethane solution having a polymer concentration of 10%.
To this solution was added 1 kg of a palladium / silica magnesia catalyst (manufactured by JGC Chemicals, palladium amount: 5% by weight), and the mixture was reacted in an autoclave at 165 ° C. for 4 hours at a hydrogen pressure of 40 kg / cm ² . The hydrogenation catalyst was removed by excess, and the polymer solution was subjected to methanol coagulation.

The specific year (η _inh ) of the obtained polymer is 0.52dl / g
(In chloroform, 30 ° C., concentration 0.5 g / dl). 60M
The olefin peak was not substantially observed on the Hz proton NMR chart, and the hydrogenation ratio was 99% or more. This polymer is called A
And

Reference Example 2 In place of Compound 1 of Reference Example 1, 2 kg of compound 1 was added.
- ethylidene - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene (hereinafter Compound 2 to) except using 3kg was conducted the same procedure as in Reference Example 1.

The intrinsic viscosity (η _inh ) of the obtained polymer was 0.52 dl / g. The hydrogenation rate was over 99%. This polymer is designated as B.

Reference Example 3 In place of Compound 1 of Reference Example 1, 800 g of Compound 1 was added.
-Methyl-5-methoxycarbonylbicyclo [2.2.1]
The same operation as in Reference Example 1 was performed, except that 200 g of hept-2-ene (hereinafter, referred to as compound 3) was used.

The intrinsic viscosity (η _inh ) of the obtained polymer was 0.52 dl / g. The hydrogenation rate was over 99%. This polymer is designated as C.

Instead of compound 1 of Reference Example 4 Reference Example 1, Compound 1 800 g, tetracyclo [4.3.1 ^2,5 .0 ^1,6] -3,7-decadiene (dicyclopentadiene, and Compound 4) 200 g The same operation as in Reference Example 2 was carried out except for using.

The intrinsic viscosity (η _inh ) of the obtained polymer was 0.52 dl / g. The hydrogenation rate was over 99%. This polymer is designated as D.

Examples 1 to 8 and Comparative Examples 1 to 8 According to the formulations shown in Table 1, after adding a metal soap of an aliphatic sulfonic acid or the like to 1 kg of the polymers A to D, molding was confirmed by injection molding.

In addition, the compounding agents 1 to 8 used in the above Examples and Comparative Examples are as follows.

Metal soap salt of aliphatic sulfonic acid; Sodium alkane sulfonate C _n H _{2n + 1} SO ₃ Na (n = 12 to 20) Metal soap release agent; Magnesium stearate Metal soap release agent; Calcium stearate higher alcohol Behenyl alcohol Oil-based release agent; 12-hydroxystearic acid triglyceride Bisamide-based release agent; Ethylene bissterinamide Monoamide-based release agent; Polyethylene glycol derivative Silicone oil-based release agent; Dimethyl polysiloxane [Effect of the Invention] The thermoplastic resin composition of the present invention exhibits good moldability. That is, the mold releasability at the time of molding is good, the occurrence of molding distortion is small, and the surface of the molded product does not peel off. In addition, the chargeability of the molded article is improved, and the attachment of dust is prevented for a long time.

This resin can be made into various molded articles by a known method, and can be applied to various uses requiring the above-mentioned features.

Specific examples include optical materials such as lenses, optical disks, optical fibers, optical waveguides, and plastic mirrors, as well as automotive materials such as automobile headlamp covers and tail lamp covers, resin plates for window glass, and carports. It can be used in a wide variety of applications such as building materials such as roofing materials and housing materials for electrical products.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-132626 (JP, A) JP-A-51-7508 (JP, A) JP-B-48-10937 (JP, B1) (58) Field (Int.Cl. ⁶ , DB name) C08L 65/00-65/04 C08K 3/00-13/08

Claims (2)

(57) [Claims] (A) opening of at least one ring-opening polymer of a norbornene derivative represented by the following general formula (1), or opening of at least one of the norbornene derivative and an unsaturated cyclic compound copolymerizable therewith; A copolymer obtained by performing ring copolymerization is hydrogenated norbornene-based resin obtained by hydrogenating 95% or more of the non-aromatic carbon-carbon double bond present in the (co) polymer. (B) 0.01 to 15 parts by weight of a metal salt of an aliphatic sulfonic acid having 10 or more carbon atoms. General formula (I) [In the formula, A and B represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X and Y represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, and a carbon atom substituted with a halogen atom. 10 hydrocarbon _{group, - (CH 2) n COOR} 1, - (CH 2) n O
COR ¹ ,-(CH ₂ ) _n CN,-(CH ₂ ) _n CONR ² R ³ ,-(CH ₂ ) _n C
_{OOZ, - (CH 2) n} OCOZ, - (CH 2) n OZ, - (CH 2) composed of _n W or X and Y, And m is 0 or 1. Note that R ¹ , R ² , R ³ and R ⁴ are a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrocarbon group or a hydrocarbon group substituted with halogen, W is SiR ⁵ _p D _3-p (R
⁵ is a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, -O
COR ⁵ or -OR ^5, p is an integer of 0 to 3), n is 0
Shows an integer of ~ 10. ] (2) at least one of X and Y in the general formula (I)
The thermoplastic resin composition according to claim 1, wherein one is a group other than a group selected from a hydrogen atom and a hydrocarbon group.