JP3250564B2 - Polycarbonate copolymer cast film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cast polycarbonate film having improved lubricity and abrasion resistance, and more particularly to a polycarbonate film having a higher concentration of siloxane constituent units in the surface layer than in the core layer. A cast film of a polysiloxane copolymer;

[0002]

2. Description of the Related Art In general, silicone oil is added or polysiloxane is blended to modify the surface properties of polycarbonate, such as its sliding properties and abrasion resistance. However, when a small amount is added, the surface modification is insufficient, and when a large amount is added, the molded product becomes cloudy and the mechanical properties (bending, tensile, etc.) are deteriorated due to poor compatibility with the polycarbonate. There are drawbacks such as

[0003]

SUMMARY OF THE INVENTION The present invention has solved these problems. That is, the present invention has the following general formula:
A cast film made of a polycarbonate-polysiloxane copolymer having the structural units represented by (A) and (B), wherein the proportion of the structural unit represented by (B) is 0.1 to 20% by weight. A polycarbonate copolymer cast film in which the concentration of the structural unit (B) in the surface layer having a depth of less than 50 mm from the film surface is at least 4 times the concentration of the structural unit (B) in the core layer having a depth of 50 mm or more.

[0004]

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(Wherein, R _{1 to} R ₈ each represent hydrogen, halogen or an alkyl group or an aryl group which may have a substituent, and R ₉ and R ₁₀ each represent hydrogen, a halogen or a substituent. And X represents an alkyl group or an aryl group,

[0006]

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Wherein R ₁₁ and R ₁₂ each represent hydrogen, halogen or an alkyl or aryl group which may have a substituent, or R ₁₁ and R ₁₂ are bonded together to form a carbon ring Or a group that forms a heterocyclic ring, and a represents one or more positive numbers. ). The proportion of structural units represented by (B) is
0.8 to 20% by weight is preferred, and the structural units (A) and (B)
Are preferably repeated at random.

Hereinafter, the configuration of the present invention will be described. The polycarbonate resin used in the present invention is a dihydric phenol represented by the following general formula (1) and a polysiloxane represented by the following general formula (2)

[0009]

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(In the general formula (1), X and R _{1 to} R ₈ represent the general formula (A)
And n represents an integer of 1 to 1000. General formula
In (2), R ₉ and R ₁₀ each represent hydrogen, halogen or an alkyl group or an aryl group which may have a substituent, and Y
Is halogen, -R ₁₃ OH, -R ₁₃ COOH, -R ₁₃ NH ₂ , -R ₁₃ NH ₂ ,
R ₁₃ represents a linear, branched or cyclic alkylidene group, an aryl-substituted alkylidene group or an aryl group; R ₁₄ represents an alkyl, alkenyl, aryl or aralkyl group; and m represents 0 or 1. ) Is copolymerized with phosgene, a carbonate ester or a chloroformate, and is a polycarbonate-polysiloxane copolymer having a proportion of the structural unit represented by the general formula (B) of 0.1 to 20% by weight. It is a polymer. When the proportion of the structural unit represented by the general formula (B) exceeds 20% by weight, the transparency is reduced,
If the amount is less than 0.8% by weight, the surface characteristics are deteriorated. The viscosity average molecular weight of the copolymer is preferably from 15,000 to 100,000. If the viscosity average molecular weight is less than 15,000, the film strength is not sufficient, and if it exceeds 100,000, the productivity tends to decrease.

The dihydric phenol represented by the general formula (1) used as the raw material for the co-polycarbonate resin of the present invention includes bis (4-hydroxyphenyl) methane and bis (4
-Hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4
-Hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2,2-
Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z
BPZ), 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy -3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-
Chlorophenyl) propane, 2,2-bis (4-hydroxy-
Examples thereof include 3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, and bis (4-hydroxyphenyl) diphenylmethane. Among them, 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane are particularly preferable.

As an example of the polysiloxane represented by the general formula (2), for example,

[0013]

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(In the general formulas (3) to (9), R ₉ and R ₁₀ are each a hydrogen, a halogen or an alkyl group or an aryl group which may have a substituent, as in the general formula (1). And R ₁₄
Represents an alkyl, alkenyl, aryl, or aralkyl group as in Y in the general formula (2), n represents an integer of 1 to 1000, and b represents a positive integer. ), Etc. Among them, α, ω-bis [3- (o-hydroxyphenyl)
Propyl] polydimethylsiloxane is particularly preferred.

The dihydric phenol represented by the general formula (2) is a phenol having an olefinic unsaturated carbon-carbon bond, preferably vinyl phenol, allyl phenol, or isopropenyl phenol, having a predetermined polymerization degree n. Can be easily produced by subjecting a polysiloxane chain having a terminal to a hydrosilation reaction.

In the production of the polycarbonate resin, a terminal terminator or a molecular weight regulator is usually used.
Examples of the terminal stopper include compounds having a monovalent phenolic hydroxyl group.In addition to ordinary phenol, p-tert-butylphenol, tribromophenol, and the like, long-chain alkylphenol, aliphatic carboxylic acid chloride, aliphatic carboxylic acid , Hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl acid esters, alkyl ether phenols and the like. The amount used is 100 to 100 moles of all dihydric phenol compounds used.
The amount is 0.5 mol, preferably 50 to 2 mol, and it is naturally possible to use two or more compounds in combination. Further, a branching agent is added to the above-mentioned dihydric phenol compound in an amount of 0.01 to 0.01%.
To 3 mol%, especially 0.1 to 1.0 mol%, to form a branched polycarbonate. As the branching agent, phloroglysin, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) can be used. ) Heptene-3,4,6-dimethyl-2,4,6-tri (4-
(Hydroxyphenyl) heptene-2,1,3,5-tri (2-hydroxyphenyl) benzol, 1,1,1-tri (4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methyl Benzyl) -4-methylphenol, polyhydroxy compounds exemplified by α, α ′, α ″ -tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, and 3,
3-bis (4-hydroxyaryl) oxindole (=
Isatin bisphenol), 5-chlorisatin, 5,7-dichlorisatin, 5-bromoisatin and the like.

The polycarbonate resin used in the present invention may contain, if desired, various additives known to the polycarbonate resin, such as reinforcing materials, fillers, stabilizers, ultraviolet absorbers, and the like. Examples include antistatic agents, lubricants, release agents, dyes, pigments, other flame retardants, and elastomers for improving impact resistance.

The solvent used in the polycarbonate resin solution of the present invention can be used as long as it dissolves the polycarbonate resin of the present invention and has an appropriate volatility. For example, halogen solvents such as chlorobenzene and methylene chloride can be used. Can be used for In consideration of safety and health at the time of casting, non-halogen solvents, especially hydrocarbon solvents exemplified by toluene, xylene, ethylbenzene and the like are preferable. The concentration of the solution is usually 1 to 30% by weight, preferably 5 to 20% by weight.

The thickness of the cast film is usually 0.1 to 10
00 μm, preferably 10-300 μm. 0.1μ thickness
If it is less than m, the strength of the film becomes insufficient, and if it exceeds 1000 μm, it becomes difficult to produce a film. In the cast film of the present invention, the concentration of the structural unit (B) in the surface layer having a depth of less than 50 ° from the film surface is at least four times the concentration of the structural unit (B) in the core layer having a depth of 50 ° or more. When the ratio of the structural unit (B) is 0.8 to 20% by weight, the concentration of the structural unit (B) in the surface layer is preferably in the range of 10 to 100% by weight.

The composition analysis of the polycarbonate-polysiloxane copolymer in the present invention at a surface layer depth of less than 50 °
C-1S, O-1S, using ESCALAB MK2 manufactured by VGScientific
Quantification was performed on Si-2P. Conditions are as follows: C, C = C, CH, C-Si peak for C (carbon), 286.1-28
A peak derived from CO of 6.2 eV, a peak derived from a carbonate bond (OCOO) of 290.5 to 290.7 eV, and a shake-up satellite peak due to a π-π ^* transition in an unsaturated bond of 291.7 to 292.3 eV were detected. For O (oxygen), C = O from 532.2 to 532.3 eV, peak derived from Si-O, 533.
A peak derived from CO of 9 to 534.0 eV was detected. Si
For (silicon) conducted a _{-O-Si (CH 3) 2} -O- ( siloxane) detection of a peak derived from 102 eV. ESCA measurement depth varies depending on atomic and electron energies, but is 100 to 600e
At C, the mean free path of C, O 2 and Si is less than 20 °, and almost no atoms at a depth of more than 50 ° are detected.
Therefore, ESCA measures the siloxane concentration below the surface layer depth of 50 °. In the analysis of a core layer with a surface layer depth of 50 mm or more, the surface was etched with argon to a depth of 50 mm.
The comparison was made by measuring the portion where the surface was shaved.

[0021]

【Example】

Example 1 To 58 liters of an 8.8% (W / V) aqueous sodium hydroxide solution, 9.12 kg of bisphenol A (BPA) and a dihydric phenol represented by the general formula (3) (R ₉ and R ₁₀ are each a methyl group, n = 41, ortho bond at b = 3) 0.595 kg (set so that the structural formula (B) becomes 5% by weight) and 10 g of hydrosulfite were added and dissolved. To this, add 36 liters of methylene chloride, and stir while keeping the temperature at 15 ° C.
144 kg was added, and then 5.3 kg of phosgene was blown in over 60 minutes. After the completion of the blowing, the mixture was vigorously stirred to emulsify the reaction solution. After emulsification, 10 mL of triethylamine was added,
The mixture was stirred and polymerized for an hour. The polymer solution was separated into an aqueous layer and an organic layer, and the organic layer was neutralized with phosphoric acid.After washing with water until the pH of the washing solution became neutral, 47 liters of isopropanol was added to precipitate the polymer. Was. The precipitate is filtered and dried to obtain a white powdery polycarbonate-polysiloxane copolymer.
(PC-Si) resin was obtained. This PC-Si resin was dissolved in the solvent chloroform, and a 120 μm thick film was produced by casting. The film was subjected to the following various tests. The results are shown in Table 1.

The siloxane concentration (% by weight) of the surface layer having a depth of less than 50 ° from the surface of the film and the siloxane concentration (% by weight) of the core layer having a depth of 50 ° or more were quantified by using the above ESCA ( C-1S, O-1S, Si-2P). The randomness of the film was evaluated by examining the presence or absence of non-uniform fibrous irregularities by TEM observation. The abrasion of the film was measured by a Taber abrasion test (load: 1 kg, CS-17 wheels, toluene atmosphere, 24 hours), and the amount of abrasion mg was measured.

Example 2 The procedure of Example 1 was repeated except that 10.72 kg of bisphenol Z (BPZ) was used instead of BPA. The results are also shown in Table 1.

Example 3 Structural formula (B) derived from the dihydric phenol represented by the general formula (3) (R ₉ and R ₁₀ are each a methyl group, n = 41 and b = 3 and an ortho bond)
Example 1 except that the concentration of
Same as. The results are also shown in Table 1.

Example 4 Structural formula (B) derived from a dihydric phenol represented by the above general formula (3) (R ₉ and R ₁₀ are each a methyl group, n = 41 and b = 3 and an ortho bond)
Example 1 except that the concentration of
Same as. The results are also shown in Table 1.

Example 5 The same as Example 1 except that the dihydric phenol represented by the general formula (3) was a compound in which R ₉ and R ₁₀ were each a methyl group, n = 41, b = 2 and a para bond. I made it. The results are also shown in Table 1.

Example 6 The same as Example 1 except that the dihydric phenol represented by the general formula (3) was a compound in which R ₉ and R ₁₀ were each a methyl group, n = 101, b = 3 and an ortho bond. I made it. The results are also shown in Table 1.

Example 7 As the dihydric phenol represented by the general formula (3), R ₉ is a methyl group,
In R ₁₀ is a phenyl group, except that used was the ortho bond n = 41, b = 3 were the same as in Example 1. The results are also shown in Table 1.

Example 8 The same procedure as in Example 1 was carried out except that the dihydric phenol represented by the general formula (4) was used in which R ₉ and R ₁₀ were each a methyl group and n = 41. I did the same. The results are also shown in Table 1.

Comparative Example 1 The procedure of Example 1 was repeated except that no dihydric phenol containing a siloxane of the general formula (2) was used. The results are also shown in Table 1.

Comparative Example 2 The procedure of Example 2 was repeated except that no dihydric phenol containing a siloxane of the general formula (2) was used. The results are also shown in Table 1.

Comparative Example 3 R ₉ and R ₁₀ are each a methyl group, n = 41, b = 3 and an ortho-bonded dihydric phenol of the general formula (3) is a structural unit in the copolymer
Example 1 except that (B) was used so as to be 0.09% by weight.
Same as. The results are also shown in Table 1.

Comparative Example 4 R ₉ and R ₁₀ are each a methyl group, n = 41, b = 3 and an ortho-bonded dihydric phenol represented by the general formula (3) is a structural unit in the copolymer.
Example 1 was repeated except that (B) was used at 25% by weight. The results are also shown in Table 1.

Comparative Example 5 The polycarbonate of Comparative Example 1 was combined with a dihydric phenol represented by the general formula (3) in which R ₉ and R ₁₀ were each a methyl group, n = 41, b = 3, and an ortho bond, and the structural formula (B) Was blended so that the ratio of the mixture was 5% by weight. The results are also shown in Table 1.

[0035]Table 1 monomer ViscosityFilm properties Formula (A) No Formula (B) No AverageSiloxane concentration OrchidAbrasion resistance Phenol^{* 1} Siloxane^{* 2} Molecular weight Depth not more than 50 mm Dam Pencil Abrasion of the full surface layersex hardness mg weight% weight% Siloxane concentration(weight%) Actual 1 BPA 95.0 5.0 3.0 × 10^Four 42 ○ 2H 12 Real 2 BPZ 95.0 5.0 3.3 × 10^Four 41 ○ 3H 11 Actual 3 BPA 99.0 1.0 3.0 × 10^Four 10 ○ 3H 14 Actual 4 BPA 80.0 20.0 3.2 × 10^Four 82 ○ 3H 12 Actual 5 BPA 95.0 5.0 3.0 × 10^Four 40 ○ 3H 12 Actual 6 BPA 95.0 5.0 3.0 × 10^Four 44 ○ 3H 11 Actual 7 BPA 95.0 5.0 3.3 × 10^Four 39 ○ 3H 13 Real 8 BPA 95.0 5.0 3.0 × 10^Four 45 ○ 3H 10 ratio 1 BPA 100.0 − 0.0 3.0 × 10^Four − ○ HB 31 ratio 2 BPZ 100.0 − 0.0 3.2 × 10^Four − ○ H 22 ratio 3 BPA 99.91 0.09 3.0 × 10^Four 0.9 ○ H 25 ratio 4 BPA 75.0 25.0 3.4 × 10^Four 85 × 3H 12 Ratio 5 BPA 95.0 ^{* 3} 5.0 3.0 × 10 ⁴ 17 × H 26 ^{* 1} BPA: Bisphenol A, BPZ: Bisphenol Z^{* 2} : R_9,R_TenAre methyl groups; n = 41, b = 3 and one of the ortho bonds
Polysiloxane of general formula (3): R_9,R_TenAre each a methyl group; n = 41, b = 2,
Polysiloxane of formula (3): R_9,R_TenAre each a methyl group; n = 101, b = 3 and the ortho bond is general
Polysiloxane of formula (3): R₉Is a methyl group_,R_TenIs a phenyl group; n = 41, b = 3 and an ortho bond
Polysiloxane of general formula (3): R_9, R_TenAre each a methyl group; n = 41
Xan^{* 3} A blend of monomers.

[0036]

According to the casting film of the polycarbonate-polysiloxane copolymer of the present invention, the polysiloxane segments are selectively gathered on the very surface (the surface layer depth is less than 50 mm), and the polysiloxane segments form the core layer having a depth of 50 mm or more. Since it is four times or more, even a small amount of polysiloxane can perform surface modification of the polycarbonate (improvement of lubrication, abrasion resistance, etc.) more than expected. In addition, the polycarbonate-polysiloxane copolymer casting film of the present invention has a good transparency without white turbidity and good mechanical properties of polycarbonate, as compared with a film made of a mixture of a polycarbonate resin and polysiloxane having the same amount of polysiloxane. It has the advantage that properties (bending, pulling, etc.) are maintained.

Claims (7)

(57) [Claims] (1) The composition has structural units represented by the following general formulas (A) and (B), and the ratio of the structural unit represented by (B) is 0.
1 to 20% by weight of a cast film made of a polycarbonate-polysiloxane copolymer, wherein structural units in a surface layer having a depth of less than 50 ° from the film surface (B)
Units in Core Layers with a Concentration of More Than 50 Depths (B)
Polycarbonate cast film having a concentration of 4 times or more of (Wherein, R _{1 to} R ₈ each represent hydrogen, halogen, or an alkyl group or an aryl group which may have a substituent, and R ₉ ,
R ₁₀ represents hydrogen, halogen, or an alkyl group or an aryl group which may have a substituent. X is Wherein R ₁₁ and R ₁₂ each represent hydrogen, halogen or an alkyl group or an aryl group which may have a substituent, or R ₁₁ and R ₁₂ are bonded together to form a carbocyclic or heterocyclic ring And a represents one or more positive numbers. ) 2. The cast film according to claim 1, wherein the film has a thickness of 10 to 300 μm. 3. The composition according to claim 1, wherein the proportion of the structural unit (B) in the polycarbonate-polysiloxane copolymer is 0.8 to 20% by weight, and the concentration of the structural unit (B) in the surface layer having a depth of less than 50 mm is 10 to 100% by weight. The cast film according to claim 1, wherein 4. The polycarbonate-polysiloxane copolymer has a viscosity average molecular weight of 15,000 to 100,000.
The described cast film. 5. A composition wherein the structural unit (A) is derived from a dihydric phenol selected from the group consisting of 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane. The cast film according to claim 1, wherein 6. The structural unit (B) is composed of α, ω-bis [3- (o-
2. The cast film according to claim 1, which is derived from [hydroxyphenyl) propyl] polydimethylsiloxane. 7. The cast film according to claim 1, wherein the polycarbonate-polysiloxane copolymer is a random copolymer.