JPH06240113A - Transparent resin composition - Google Patents

Abstract

PURPOSE:To obtain a cyclic olefinic composition having excellent heat resistance, toughness and transparency. CONSTITUTION:100 pts.wt. of (a) a cyclic polyolefinic resin is mixed with 1 to 70 pts.wt. of (b) a glass having a refractive index (nD<25>) of that of the cyclic polyolefin resin + or - 0.02 to give the objective transparent resin composition high in heat resistance, toughness and transparency.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent resin composition having high heat resistance and rigidity, and more specifically, to high rigidity without impairing the excellent optical properties and heat resistance of cyclic olefin resin. The present invention relates to a transparent resin composition that dramatically improves the industrial utility of cyclic olefins.

[0002]

2. Description of the Related Art In recent years, a cyclic olefin resin has attracted attention as a heat-resistant transparent thermoplastic resin. Cyclic polyolefin resins are disclosed in JP-A-1-36615, JP-A-61-292201, and JP-A-63-2187.
No. 26, JP-A-2-133413 and the like. These resins have an aliphatic main chain and characteristically contain an aliphatic polycyclic ring structure in the main chain. The cyclic polyolefin-based resin has a high glass transition temperature due to the rigidity of the main chain structure, bulkiness of the main chain structure hinders crystallization, and high transparency due to being amorphous, due to the ring structure, The direction of covalent bond becomes random with respect to the main chain direction, and there is almost no anisotropy of polarizability per repeating unit of the polymer, and by extension, the compound refraction does not occur due to the orientation during molding. It has excellent mechanical and optical properties such as a low birefringence index.
As described above, the cyclic polyolefin resin is superior in heat resistance and has a low birefringence index as compared with the conventional typical transparent thermoplastic resins such as polymethylmethacrylate (PMMA) and polycarbonate (PC). It is used for materials.

[0003]

However, the cyclic olefin resin may not be adopted because of insufficient rigidity. The present invention has been made based on the above circumstances, the object is to reliably exhibit excellent heat resistance, compared to the glass fiber composite resin until now,
An object of the present invention is to provide a composition exhibiting excellent transparency having a higher elastic modulus.

[0004]

According to the present invention, 100 parts by weight of a cyclic polyolefin resin (a) has a refractive index (n _D ²⁵ ).
A transparent resin composition comprising 1 to 70 parts by weight of the glass (b) in the range of (n _D ²⁵ ) ± 0.02 of the cyclic polyolefin resin, wherein 100 parts by weight of the composition of claim 1 is refracted. The ratio (n _D ²⁵ ) of the cyclic polyolefin resin is n _D ²⁵ ±
A transparent resin composition containing 1 to 40 parts by weight of the rubbery polymer (c) in the range of 0.02, 100 parts by weight of the composition of claim 1 or 2 of the composition of claim 2 has a refractive index ( n _D ²⁵ ) is a cyclic polyolefin resin n _D ²⁵ ± 0.
The present invention provides a transparent resin composition containing 0.5 to 20 parts by weight of the phosphorus-based flame retardant (d) in the range of 02. The cyclic polyolefin-based resin applied to the transparent resin composition of the present invention has a saturated aliphatic main chain, and is characterized by containing an aliphatic polycyclic cyclic structure in the main chain, but specific examples thereof Is a compound having a norbornane skeleton in its repeating unit. For example, as the cyclic polyolefin-based resin, general formulas (I) to (I
There may be mentioned a thermoplastic resin composition containing a norbornane skeleton represented by V).

[0005]

[Chemical 1]

[0006]

[Chemical 2]

[0007]

[Chemical 3]

[0008]

[Chemical 4]

[In the formula, A, B, C and D are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom,
^{_{(CH 2) n COOR 1,}} - (CH 2) n OCOR 1,
^{_{- (CH 2) n OR 1}} , - (CH 2) n CN, - (CH
₂ ) _n CONR ³ R ² ,-(CH ₂ ) _n COOZ,-
_{(CH 2) n OCOZ, -} (CH 2) n OZ, - (CH
₂ ) _n W, or composed of B and C Alternatively, it represents a (poly) cyclic alkylene group. here,
R ¹ , R ² , R ³ and R ⁴ are hydrocarbon groups having 1 to 20 carbon atoms, Z is a hydrocarbon group substituted with a halogen atom, W is SiR ⁵ _p F _3-p [R ⁵ is 1 carbon atom 10 to 10 hydrocarbon groups, F is a halogen atom, -OCOR ⁶ or -OR
⁶ (R ⁶ represents a hydrocarbon group having 1 to 10 carbon atoms), p
Represents an integer of 0 to 3. ], N shows the integer of 0-10. ]

Examples of the cyclic polyolefin resin having a norbornane skeleton which can be used in the present invention include, for example, JP-A-60-168708, JP-A-62-252406 and JP-A-62-252407.
JP-A No. 2-133413, JP-A No. 63-
145324, JP-A-63-264626, JP-A-1-240517, and JP-B-57-88.
Examples thereof include resins described in Japanese Patent Publication No. 15 and the like. Specific examples of the cyclic polyolefin-based resin include metathesis polymerization of at least one tetracyclododecene derivative represented by the following general formula (V) or an unsaturated cyclic compound copolymerizable with the tetracyclododecene. The hydrogenated polymer obtained by hydrogenating the obtained polymer can be mentioned.

[0011]

[Chemical 5]

(In the formula, A to D are the same as above.) In the tetracyclododecene derivative represented by the general formula (V), it is necessary that A, B, C and D contain a polar group. Is preferable because it is excellent. Further, the polar group - (CH ₂₎ a group represented by _n COOR ¹ is preferred in that the resulting hydrogenated polymer is to have a high glass transition temperature. In particular, this- (C
The polar substituent consisting of the group represented by H ₂ ) _n COOR ¹ is contained in one molecule of the tetracyclododecene derivative represented by the general formula (V), so that the resulting hydrogenated polymer has high heat resistance. It is preferable in that the hygroscopicity can be lowered while maintaining the property. Further, among the groups represented by — (CH ₂ ) _n COOR ¹ , those having a smaller value of n are preferable because the glass transition temperature of the obtained hydrogenated polymer is further increased.

In the above general formula, R ¹ has 1 to 2 carbon atoms.
Although it is a hydrocarbon group of 0, it is preferable as the number of carbon atoms increases so that the hygroscopic property of the obtained hydrogenated polymer decreases.
From the viewpoint of the balance with the glass transition temperature of the obtained hydrogenated polymer, a chain alkyl group having 1 to 4 carbon atoms or a (poly) cyclic alkyl group having 5 or more carbon atoms is preferable, and a methyl group or ethyl group is particularly preferable. And a cyclohexyl group are preferred. Furthermore, - (CH _{2) n} to a carbon atom group is bonded represented by COOR ^1, simultaneously tetracyclododecene derivatives of the general formula is a hydrocarbon group having 1 to 10 carbon atoms which is bonded as a substituent (V) Is preferable because it lowers the hygroscopicity without lowering the glass transition temperature of the obtained hydrogenated polymer. In particular, the tetracyclododecene derivative represented by the general formula (V) in which the substituent is a methyl group or an ethyl group is preferable because the synthesis thereof is easy. These tetracyclododecene derivatives or a mixture of unsaturated cyclic compounds copolymerizable therewith are described, for example, in JP-A-4-7752.
According to the method described in No. 0, page 12, line 12, page 22, line 6, metathesis polymerization and hydrogenation can be carried out to obtain the polyolefin resin used in the present invention.

In the present invention, the hydrogenated polymer used as the cyclic polyolefin resin has an intrinsic viscosity ([η] _inh ) of 0.
It is preferably in the range of 3 to 1.5 dl / g.
When [η] _inh is within the above range, molding processability, heat resistance, water resistance, chemical resistance, mechanical properties and the like are good. The hydrogenation rate of the hydrogenated polymer is 60 MH.
The value measured by z, ¹ H-NMR is 50% or more, preferably 90% or more, more preferably 98% or more. The higher the hydrogenation rate, the better the stability to heat and light.

As the component (b) glass, the glass fiber (L; average length, D; average diameter) having a refractive index (n _D ²⁵ ) in the range of n _D ²⁵ ± 0.02 of the cycloolefin resin. , L / D is more than 1), flakes (L / D is less than 1), beads (L / D =
1) etc. can be mentioned. Further, these glasses can be used together. When the glass fiber having a large L / D is used here, the rigidity of the obtained composition is further excellent, but the warpage and the sink mark are large. Further, when the flakes and beads having a small L / D are used, the rigidity of the obtained composition does not become so large, but the warpage and sink marks are small and the appearance is good. As a concrete example, when a high-strength glass fiber called T-glass (n _D = 1.523) is compounded with (a) a cyclic olefin resin, the E-glass fiber used until now is The strength and elastic modulus of the obtained composition are improved as compared with the composite material. Further, in the present invention, C glass (n _D =
Fibers such as 1.51) and S-glass (n _D = 1.52) can also be used. The glass fibers and flakes used in the present invention may be coated, and the same coating agent as that for ordinary (E-glass) can be used. The content of the glass (b) in the transparent resin composition of the present invention is 1 to 70 parts by weight, preferably 5 to 60 parts by weight, more preferably 10 to 50 parts by weight, relative to 100 parts by weight of the component (a). Is. (B) If it exceeds 70 parts by weight, moldability and impact resistance are lowered.

Component (c) In the transparent resin composition according to the present invention, a rubbery polymer (c) that is particularly preferable for obtaining a resin having excellent transparency is a random copolymer of hydrogenated styrene-butadiene. A copolymer, a block copolymer or a block-random copolymer having a styrene content of 20 to 45% by weight, and a copolymer of butadiene and an acrylic ester, wherein Examples thereof include those having a weight ratio of 10 to 90:90 to 10, those in which 100 parts by weight of these are copolymerized with 0 to 30 parts by weight of styrene and / or acrylonitrile, and hydrogenated products thereof. it can. The rubbery polymer (c) is an epoxy group, a carboxyl group, or an epoxy group for the purpose of improving the compatibility with the cyclic olefin resin (a).
It may be modified with a specific functional group such as a hydroxyl group, an amino group, an acid anhydride group and an oxazoline group. The rubbery polymer (c) in the transparent resin plastic material of the present invention is 1 to 40 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the total of the components (a) and (b). It is more preferably 8 to 25 parts by weight. If it exceeds 40 parts by weight, the rigidity becomes low.

Examples of the phosphorus-based flame retardant (d) include aromatic condensed phosphoric acid esters, preferably triphenyl phosphate. In order to make the transparent resin composition of the present invention flame-retardant, 100 parts by weight of the phosphorus-based flame retardant having a refractive index within the range of the refractive index (n _D ²⁵ ) of the cyclic olefin resin ± 0.02 is used. 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight,
It is more preferably 2 to 13 parts by weight. When the amount of the phosphorus-based flame retardant (d) used exceeds 20 parts by weight, the heat resistance of the composition decreases. . INDUSTRIAL APPLICABILITY The transparent resin composition of the present invention can be suitably used as an automobile part such as a tail lamp and a head lamp, a building material such as a glazing, a greenhouse and an aquarium, and an electronic material such as a sealing material.

[0018]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In the examples, parts and% are based on weight unless otherwise specified. Further, various measurements in the examples are as follows.

Heat resistance ; heat distortion temperature (HDT), AST
According to MD648, using a test piece with a thickness of 1/2 ",
The load was measured at 66 psi. Rigidity ; using test pieces (3/2 "x 1/8" x 5 "),
The flexural modulus (FMo) was measured according to ASTM D790. Fluidity : 280 ° C x 10 according to JIS K7210
The melt flow rate (MFR) was measured under the conditions of kg. Transparency (total light transmittance) (Tt) : ASTM D100
3 Appearance : The obtained test piece was visually evaluated, and it is shown as excellent ⊚, good ∘, and bad x. Flame retardance : UL94 test

Preparation of Reference Example (a) Component (a) -1 (hydrogenated norbornene-based resin): 8-methyl-8-methoxycarbonyltetracyclo [4.4. 0.1 ^2,5 . 1
^7,10 ] -3-dodecene (500 g), 1,2-dichloroethane (2,000 ml), 1-hexene (3.8 g), which is a molecular regulator, and a tungsten hexachloride concentration of 0.1.
91.6 ml of 05 mol / liter chlorobenzene solution
And a paraaldehyde concentration of 0.1 mol / l
By adding 68.7 ml of a 2-dichloroethane solution and 37 ml of a toluene solution of triisobutylaluminum having a concentration of 0.5 mol / liter and reacting at 60 ° C. for 10 hours, an intrinsic viscosity [η] _inh of 0.56 dl / g 450 g of a polymer (in chloroform, 30 ° C., concentration 0.5 g / dl) was obtained. This polymer was dissolved in 9,000 ml of tetrahydrofuran, charged into a high-pressure reactor, 45 g of a palladium-alumina catalyst having a palladium concentration of 5% was added as a hydrogenation catalyst, and hydrogen gas was supplied at a pressure of 100 kg / cm.
^The mixture was charged to ² and hydrogenated at 150 ° C. for 5 hours. After the hydrogenation reaction, the catalyst was filtered off, and the solution was poured into a large excess of hydrochloric acid-acidified methanol to obtain hydrogenated norbornene-based resin (a) -1. The hydrogenation rate of this hydrogenated nonebornene resin (a) -1 was substantially 100%, and the refractive index (n _D ²⁵ ) was 1.511.

(B) Component T glass fiber [manufactured by Nittobo Co., Ltd.], n _D ²⁵ = 1.52,
Average diameter 13 μm T glass flake (d = 230 μm) prototype, n _D ²⁵ =
1.52 T glass beads (d = 30 μm) prototype, n _D ²⁵ = 1.
52 E glass fiber (manufactured by Nittobo Co., Ltd.), n _D ²⁵ = 1.56,
Average diameter 13 μm C glass fiber [manufactured by Nippon Glass Co., Ltd.], n _D ²⁵ = 1.5
1, average diameter 19 μm S glass fiber [manufactured by Asahi Fiber Co., Ltd.], n _D ²⁵ = 1.5
2, average diameter 13μm

Production of component (c) -1 (hydrogenated block copolymer): An autoclave having an internal volume of 5 liters was charged with 2,500 g of degassed and dehydrated cyclohexane and 100 g of styrene, and then tetrahydrofuran 9 0.8 g and n-butyllithium 0.2 g were added, and isothermal polymerization was performed at 50 ° C. (first stage polymerization). After the polymerization conversion rate became almost 100%, 325 g of 1,3-butane and 7 parts of styrene were continuously added.
Polymerization was carried out at 70 ° C. while continuously adding 5 g of the mixture at a rate of 75 g per 10 minutes. (Second stage polymerization). After the polymerization conversion rate of the added monomer reached almost 100%, the reaction liquid was cooled to 70 ° C., and 0.6 g of n-butyllithium and 0.6 g of 2,6-t-butylcresol.
Then, 0.28 g of bis (cyclopentadienyl) titanium dichloride and 1.1 g of diethylaluminum were added, and a hydrogenation reaction was carried out for 1 hour while maintaining hydrogen gas at a pressure of 1.0 kg / cm ² .

Next, the reaction solution was cooled to room temperature, taken out from the autoclave, desolvated by steam stripping, dried on a roll at 120 ° C., and the following hydrogenated block copolymer (b)- Got 1. Total bound styrene content (%) 35 Ratio of first-stage polymer block to total copolymer (%) 20 Vinyl bond content of butadiene portion in block copolymer (%) 40 Hydrogenation ratio (%) 98 minutes Content (1 × 10 ⁴ ) 16 Melt flow rate (230 ° C., 5 kg, unit = g / 10 minutes) Deflection rate (n _D ²⁵ ) 1.515 (d) Component triphenyl phosphate (described as TPP) used

Examples 1 to 4 and Comparative Example 1 As shown in Table 1, the amount of glass fiber was varied to 4
Pellets were produced with a 0 m / m extruder (280 ° C.), and the pellets were injected into an injection molding machine (TOSHIBA MACHINE CO., LTD. IS 12
5A) was used to prepare a test piece at an injection molding temperature of 300 ° C., and the physical properties were measured. The results are shown in Table 1. Examples 4, 5 and Comparative Example 2 Test pieces were prepared in the same manner as in Example 1 except that the amount of the rubbery polymer was varied as shown in Table 1, and the physical properties were measured. Examples 6 and 7, Comparative Example 3 Example 1 except that the amount of TPP was varied as shown in Table 1.
A test piece was prepared in the same manner as above, and the physical properties were measured. The results are shown in Table 1.

[0025]

[Table 1]

Examples 8 and 9, Comparative Example 4 Example 1 except that the type of glass was changed as shown in Table 2.
A test piece was prepared in the same manner as above, and the physical properties were measured. The results are shown in Table 2.

[0027]

[Table 2]

Implementation Orders 10 and 11 Example 1 except that the type of glass was changed as shown in Table 3.
A test piece was prepared in the same manner as above, and the physical properties were measured. The results are shown in Table 3.

[0029]

INDUSTRIAL APPLICABILITY The present invention is a transparent resin composition having high heat resistance and rigidity, which is effective for electric / electronic and OA machine parts.

Claims (3)

[Claims] 1. A cyclic polyolefin resin (a) 100.
Glass (b) 1 having a refractive index (n _D ²⁵ ) in the range of (n _D ²⁵ ) ± 0.02 of the cyclic polyolefin resin in parts by weight.
A transparent resin composition containing about 70 parts by weight. 2. 100 parts by weight of the composition according to claim 1,
Refractive index (n _D ²⁵ ) of cyclic polyolefin resin n _D ²⁵
Rubber polymer (c) in the range of ± 0.02 is 1 to 40
A heat-resistant, high-rigidity, impact-resistant transparent resin composition prepared by blending parts by weight. 3. A phosphorus-based compound having a refractive index (n _D ²⁵ ) of 100 parts by weight of the composition of claim 1 or the composition of claim 2 in the range of n _D ²⁵ ± 0.02 of the cyclic polyolefin resin. A transparent resin composition containing 0.5 to 20 parts by weight of a flame retardant (d).