JP2003313432A - Lubricant for synthetic resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lubricant for a synthetic resin satisfactory in both moldability and transparency, and a synthetic resin composition containing the same. <P>SOLUTION: This lubricant for a synthetic resin comprises an anionic surfactant which has an anionic group and at least one group selected from among -(AO)<SB>n</SB>- groups (wherein A is a 2-4C alkylene group; and n is such a number that the AO fraction in the molecule is 10-80% and each of n A's may be the same or different from each other) and aromatic rings. The synthetic resin composition contains the lubricant and a synthetic resin. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a lubricant for synthetic resins,
It also relates to a synthetic resin composition having excellent moldability and transparency.

[0002]

BACKGROUND OF THE INVENTION Amides, hydrocarbon waxes, ester waxes, fatty acids, fatty acid esters, phosphoric acid esters, metal soaps, etc. are known as lubricants for synthetic resins. Has been.

Among the synthetic resins, an amorphous polyester resin is particularly used as a material for various films and sheets, and has better processability than ordinary polyester resins and can be calendered. Have.
As a lubricant for such an amorphous polyester resin, for example, JP-A-11-343353 discloses a fatty acid ester lubricant such as stearic acid monoglyceride, but the roll releasability in calendar molding is not sufficient. Further, JP-A No. 2000-302951 discloses a phosphate ester lubricant such as mono (di) stearyl phosphate ester, but there is a problem in the transparency of the resin. Further, Japanese Patent Laid-Open No. 2000-327891 discloses a montanic acid wax which is an ester wax lubricant, but this also does not have sufficient roll releasability in calender molding.

Therefore, no lubricant has been obtained which satisfies both processability, particularly roll releasability during calendar processing and resin transparency.

An object of the present invention is to provide a synthetic resin lubricant and a synthetic resin composition which satisfy both molding processability and transparency.

[0006]

The present invention has the following intramolecular structure:
(AO) _n- (A is an alkylene group having 2 to 4 carbon atoms, n is a number at which the AO fraction in the molecule is 10 to 80%, and n A's may be the same or different) A synthetic resin lubricant comprising an anionic surfactant having at least one selected from a group represented by a polyoxyalkylene group (hereinafter referred to as a polyoxyalkylene group) or an aromatic ring, and this lubricant,
A synthetic resin composition containing a synthetic resin is provided.

Here, the AO fraction is the ratio (%) of the polyoxyalkylene group portion to the molecular weight of the compound.
Say.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION [Lubricant] The lubricant of the present invention is an anionic surfactant having at least one selected from a polyoxyalkylene group or an aromatic ring and an anionic group in the molecule.

In the polyoxyalkylene group, examples of A include an ethylene group, a propylene group and a butylene group, and an ethylene group is preferable from the viewpoint of transparency. n is the average number of moles of alkylene oxide added, and A in the molecule
The O fraction is 10 to 80%, preferably 20 to 80%, and more preferably 25 to 80%.

Examples of the aromatic ring include a benzene ring and a naphthalene ring. Examples of the group having an aromatic ring include a phenyl group, a benzyl group, an alkylphenyl group (having 1 to 22 carbon atoms in the alkyl group) and an alkylbenzyl group (alkyl). Group having 1 to 22 carbon atoms, naphthyl group, alkylnaphthyl group (alkyl group having 1 to 18 carbon atoms), and the like. From the viewpoint of transparency, a phenyl group, a benzyl group, an alkylphenyl group (carbon of an alkyl group). The numbers 1 to 18) are preferable.

[0011] Examples of the anionic group, -SO ₃ ^-, -S
O ₄ ⁻ , —COO ^{−, and the} like, and from the viewpoint of lubricity, —S
O ₃ ⁻ and —SO ₄ ⁻ are preferable, and —SO ₃ ⁻ is more preferable.
Further, as counter ions of these anion groups, Li, N
Examples include cations such as a, K, Ca, Mg, Al, and Zn. From the viewpoint of lubricity and transparency, Na, Al, and Zn are preferable, and Na is more preferable.

Examples of the anionic surfactant of the present invention include alkyl (C1 to C22) benzenesulfonate, polyoxyalkylene (AO fraction 10 to 80%) alkyl or alkenyl (carbon number of alkyl group or alkenyl group). 6
~ 22) ether sulfate, polyoxyalkylene (AO
Fraction 10 to 80%) Alkyl or alkenyl (C6 to C22 alkyl group or alkenyl group) ether acetate, di [polyoxyalkylene (AO fraction 10 to 80)
%) Phenyl ether] sulfosuccinate, di [polyoxyalkylene (AO fraction 10 to 80%) phenyl ether] succinate, and the like, and from the viewpoint of compatibility,
Alkyl (C8-18) benzene sulfonate, polyoxyethylene (hereinafter referred to as POE) lauryl ether acetate (AO fraction 40-70%), di [POE phenyl ether] sulfosuccinate (AO fraction 30- 70
%), POE oleyl ether sulfate (AO fraction 50-
80%) is preferred, especially alkyl (C8-18)
Benzene sulfonate and POE lauryl ether acetate (AO fraction 40 to 70%) are preferable. Incidentally, unneutralized ones are not preferable because they have no slipping effect.

[Synthetic Resin] Examples of the synthetic resin according to the present invention include polyester resin, ABS resin, polycarbonate resin, acrylic resin, polyvinyl chloride resin and the like. Polyester resin is preferable, and amorphous polyester resin is particularly preferable. Is preferred.

The amorphous polyester resin has a lower processing temperature than that of a normal polyester resin having a processing temperature of 270 to 280 ° C., and is not higher than 200 ° C., preferably 16
It can be processed even under conditions of 0 to 190 ° C, has good workability, and can be calendered. Here, the processing temperature means a temperature at which the resin can be molded, and for example, in the case of a calendering method, it corresponds to the temperature of the roll surface at which the resin can be molded.

Specific examples of the amorphous polyester resin include (A) terephthalic acid or a lower alkyl ester thereof (alkyl group having 1 to 3 carbon atoms, such as dimethyl terephthalate) (hereinafter referred to as component (A)), (B) ethylene glycol (hereinafter referred to as "component (B)"), and (C) dicarboxylic acid other than terephthalic acid or lower alkyl ester thereof or lower alkyl ester thereof (alkyl group having 1 to 3 carbon atoms) (hereinafter component (C)) A polyester resin obtained by copolymerizing a component (A), a component (B), and a glycol component other than ethylene glycol (D) (hereinafter referred to as a component (D)); ) Component, (B) component, (C) component, and (D)
Examples thereof include polyester resins obtained by copolymerizing the components.

Examples of the component (C) include one or more selected from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, aliphatic dicarboxylic acids and lower alkyl esters thereof, and the aromatic dicarboxylic acids include Isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,
5-naphthalenedicarboxylic acid, bis (4,4′-carboxyphenyl) methane, anthracene dicarboxylic acid,
4,4'-diphenyl ether dicarboxylic acid etc. are mentioned. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid and 4,4′-dicyclohexyldicarboxylic acid. Examples of the aliphatic dicarboxylic acid include adipic acid, sebacic acid, azelaic acid, dimer acid and the like. Among these components (C), isophthalic acid and its lower alkyl ester are preferred.

As the component (D), 1,4-cyclohexanedimethanol, propylene glycol, 1,5
-Pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, 4,
4'-dicyclohexyl hydroxymethane, 4,4'-
One or more selected from dicyclohexyl hydroxypropane, bisphenol A ethylene oxide addition diol, polyethylene oxide glycol, polypropylene oxide glycol and the like can be mentioned.

The dicarboxylic acid component in the amorphous polyester resin according to the present invention is preferably 60 mol% or more of the aromatic dicarboxylic acid component, more preferably 60 mol% or more of the component (A). The glycol component is preferably 60 mol% or more of the component (B).

The glass transition temperature of the amorphous polyester resin according to the present invention is preferably 50 to 85 ° C., and 60 to 85.
C is even more preferred.

As the amorphous polyester resin according to the present invention, TSUNAMI G manufactured by Eastman Chemical Company is used.
S1, GS2, GS3, GS4, etc. can be used.

[Synthetic Resin Composition] The synthetic resin composition of the present invention contains the lubricant of the present invention as described above and a synthetic resin. The content of the lubricant of the present invention is preferably 0.05 based on 100 parts by weight of the synthetic resin in terms of processability and transparency in both cases of calendar molding and extrusion molding.
-5 parts by weight, more preferably 0.1-3 parts by weight, and particularly preferably 0.5-2 parts by weight. In addition, in these molding methods, as a method of adding the lubricant of the present invention, in addition to the method of directly adding to the resin, a method of using a masterbatch in which the resin and the lubricant are mixed in advance can be mentioned. In that case, the ratio of the lubricant to 100 parts by weight of the synthetic resin is preferably 5 to 40 parts by weight, more preferably 7 to 30 parts by weight, and particularly preferably 10 to 20 parts by weight.

The composition of the present invention preferably further contains a plasticizer. Examples of the plasticizer include the following. Ester of the following (a) component and (b) component (a) General formula (I)

[0023]

[Chemical 1]

(In the formula, X ¹ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 22 carbon atoms, an alkenyl group or an alkoxy group, or a halogen atom, n and m are each an integer of 1 or more, and n + m = 5. And p represents an integer of 0 to 3. m X ^1's may be the same or different.)
A hydroxy aromatic carboxylic acid represented by 1 in one molecule
Hydroxy-fused polycyclic aromatic carboxylic acids having one or more hydroxyl groups and carboxyl groups, hydroxyalicyclic carboxylic acids, or anhydrides of these carboxylic acids or having 1 to 1 carbon atoms
At least 1 selected from 3 lower alkyl esters
seed. (B) A hydroxy compound selected from aliphatic alcohols, alicyclic alcohols, aromatic alcohols, phenols and alkylphenols, or an alkylene oxide adduct of these hydroxy compounds (having 2 to 4 carbon atoms in the alkylene group and an average addition mole of alkylene oxide). At least one selected from the number 0 and 30 or less). Ester (c) of the following component (c) and component (d)
General formula (II)

[0025]

[Chemical 2]

(In the formula, X ² represents a hydrogen atom, a methyl group or a halogen atom, q and r are each an integer of 1 or more, and q + r = 6. Q pieces of X ² may be the same or different. An aromatic carboxylic acid represented by the formula (1), a condensed polycyclic aromatic carboxylic acid having one or more carboxyl groups in one molecule, an alicyclic carboxylic acid, or an anhydride of these carboxylic acids or having 1 to 1 carbon atoms. At least one selected from the lower alkyl ester of 3. (D) Aliphatic monoalcohol, alicyclic monoalcohol,
At least one selected from alkylene oxide adducts of monohydroxy compounds selected from aromatic monoalcohols, phenols, and alkylphenols (alkylene groups having 2 to 4 carbon atoms and alkylene oxide average addition mole numbers of 1 to 30). N-alkylated aromatic sulfonamide (alkyl group having 1 to 22 carbon atoms) Ester of the following (e) component and (f) component (e) General formula (III)

[0027]

[Chemical 3]

(In the formula, X ³ is a hydrogen atom and has 1 to 22 carbon atoms.
Alkyl group, alkenyl group or alkoxy group, or a halogen atom, s represents an integer of 1 to 5, and s X ³
May be the same or different. Of an aromatic monocarboxylic acid represented by), a linear or branched aliphatic monocarboxylic acid having 1 to 22 carbon atoms, a condensed polycyclic aromatic monocarboxylic acid, an alicyclic monocarboxylic acid or a monocarboxylic acid thereof. At least one selected from lower alkyl esters (alkyl group having 1 to 3 carbon atoms). (F) General formula (IV)

[0029]

[Chemical 4]

(In the formula, Y and Z represent an alkyl group or an alkenyl group having 1 to 8 carbon atoms and may be the same or different.) Aliphatic dihydric alcohol, 3 in one molecule An alkylene oxide adduct of a hydroxy compound selected from the above polyhydric alcohols having a hydroxyl group and having 3 to 30 carbon atoms and an alicyclic diol having two hydroxyl groups or a methylol group in one molecule (the number of carbon atoms of the alkylene group is 2 To 4, at least one alkylene oxide average addition mole number per hydroxyl group, which is greater than 0 and 10 or less). Aliphatic dicarboxylic acid polyoxyalkylene alkyl ether ester, polyalkylene glycol fatty acid ester, or ester of aliphatic polyhydric alcohol and benzoic acid As the above ester, the component (a) is p-hydroxybenzoic acid or salicylic acid, The component (b) is represented by the general formula (V) R ¹ O (AO) _y H (V) (In the formula, R ¹ is a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or a phenyl group. A benzyl group or an alkylphenyl group or an alkylbenzyl group having an alkyl group having 1 to 18 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, and y is an alkylene oxide having an average addition mole number of 0 to 30. Is a number, and y is A
May be the same or different. ) A compound represented by
Alternatively, the number of carbon atoms having 3 or more hydroxyl groups in one molecule is 3 to 3
Alkylene oxide adduct of polyhydric alcohol of 0 (carbon number of alkylene group is 2 to 4, average number of moles of alkylene oxide added per hydroxyl group is greater than 0 and 10 or less)
Preferred are the esters obtained from the combination

As the above ester, the component (c) is benzoic acid, phthalic acid, terephthalic acid, trimellitic acid,
Pyromellitic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid or their anhydrides or carbon number 1
Is a lower alkyl ester of 3 to 3 and the component (d) is represented by the general formula (VI) R ² O (AO) _z H (VI) (wherein R ² is a linear or branched alkyl group having 1 to 22 carbon atoms). Or an alkenyl group, a phenyl group, a benzyl group or an alkylphenyl group having an alkyl group having 1 to 18 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, and z is an average addition mole number of alkylene oxide 1 to It is a number of 30, and z A's may be the same or different.)
The ester obtained from the combination which is a compound represented by

The N-alkylated aromatic sulfonamide is represented by the general formula (VII)

[0033]

[Chemical 5]

(In the formula, R ³ represents a linear or branched alkyl group having 1 to 22 carbon atoms.) N-alkylbenzenesulfonamide is preferable.

Examples of the above-mentioned ester include benzoic acid which component (e) may have an alkyl group having 1 to 6 carbon atoms or a halogen atom as a substituent, or a lower alkyl ester thereof (having 1 to 6 carbon atoms in the alkyl group). 3) and
(F) component is neopentyl glycol, 2-butyl-2
-Ethyl-1,3-propanediol, glycerin, sorbitol, sorbitan, trimethylolpropane, pentaerythritol, cyclohexanediol, cyclohexanedimethanol ethylene oxide adduct (average number of moles of ethylene oxide added per hydroxyl group is greater than 0). Esters obtained from combinations of 10 or less) are preferred.

As the above-mentioned ester, dipropylene glycol dibenzoate, ethylene glycol dibenzoate, neopentyl glycol dibenzoate, polyoxyethylene methyl ether adipic acid diester and the like are preferable.

The content of these plasticizers is 10
It is preferably 1 to 70 parts by weight, more preferably 3 to 50 parts by weight, and particularly preferably 5 to 30 parts by weight, relative to 0 parts by weight.

The composition of the present invention comprises, in addition to the above components, an antistatic agent, an antifogging agent, a light stabilizer, an ultraviolet absorber,
A pigment, an inorganic filler, an antifungal agent, an antibacterial agent, a foaming agent, a flame retardant and the like can be contained within a range not hindering the achievement of the object of the present invention.

The synthetic resin composition of the present invention has good moldability, and in particular, since the amorphous polyester resin composition can be processed at a low temperature such as 160 to 190 ° C., it can be calendered. And also has good transparency. The composition of the present invention can be molded into a film or sheet and used for various purposes.

[0040]

EXAMPLES Example 1 Amorphous polyester resin (TSUNAMI GS2: Eastman Chemical Co., glass transition temperature 81 ° C.) 10
0.8 parts by weight of the lubricant shown in Table 1 was added to 0 parts by weight to obtain an amorphous polyester resin composition. The obtained composition was evaluated for lubricity and transparency by the following methods. The results are shown in Table 1.

<Evaluation Method of Lubricity> The resin composition was put into a 6-inch roll shown in FIG. 1 having a roll temperature of 160 ° C., a rotation speed of 20 r / m, and a gap of 1 mm, kneaded for 15 minutes, and then peeled off from the roll. The peelability from the roll was evaluated from the peeling position shown in FIG. 1 according to the following criteria.

Peeling position 0: The sheet cannot be peeled off from the roll and cannot be operated Peeling position 1: The sheet is very difficult to peel off from the roll,
Peeling position where the workability is extremely poor 2: The sheet is difficult to peel off from the roll, but work can be performed Peeling position 3: The sheet is slightly difficult to peel off from the roll,
Workability is good Peeling position 4, 5: The sheet is easily peeled off from the roll and has moderate wrapping, so workability is very good Peeling position 6: Peeling position of the sheet on the roll is poor and workability is slightly poor 7: Sheet is not wound around roll and cannot be kneaded <Evaluation method of transparency> The composition is kneaded with a 6-inch roll at 160 ° C for 15 minutes, and a test piece having a thickness of 1 mm is obtained by a press molding machine at 190 ° C. Created. The haze value of this test piece was measured with a haze meter. The smaller the number, the better the transparency.

[0043]

[Table 1]

* 1: Compound represented by the following formula

[0045]

[Chemical 6]

* 2: One synthesized by the following method, in a 500 mL four-necked flask, stearyl alcohol 3
Charge 24.0 g (1.2 mol), and under nitrogen blowing,
It heated up to 80 degreeC and melted. 56.8 g (0.
(4 mol) diphosphorus pentoxide was gradually added and stirred until uniform. Then, the temperature was raised to 120 ° C. and aging was continued for 8 hours to obtain a mixture in which the molar ratio of monostearyl phosphate ester and distearyl phosphate ester was 1: 1.

Example 2 Amorphous polyester resin (TSUNAMI GS2: Eastman Chemical Co., glass transition temperature 81 ° C.) 10
0.8 parts by weight of the lubricant shown in Table 2 and 20 parts by weight of the plasticizer shown in Table 2 were added to 0 parts by weight to obtain an amorphous polyester resin composition. The obtained composition was evaluated for lubricity and transparency in the same manner as in Example 1. The results are shown in Table 2.

[0048]

[Table 2]

[0049]

EFFECTS OF THE INVENTION The lubricant of the present invention, when incorporated into a synthetic resin, imparts excellent roll releasability without inhibiting gelation or plate out during molding and maintains excellent transparency. A synthetic resin composition having excellent bloom resistance and bleed resistance can be obtained. Especially as a synthetic resin,
When the amorphous polyester resin is used, excellent processability and product properties are imparted during calendar molding, and the composition of the present invention containing a plasticizer further imparts excellent roll peelability and transparency, and the molded article is It has excellent transparency and heat resistance.

[Brief description of drawings]

FIG. 1 is a schematic view of a roll used for evaluation of lubricity in Examples.

Continued front page    F term (reference) 4J002 BD021 BG031 BN141 CF041                       CF051 CF061 CF071 CF081                       CG001 CH052 FD172

Claims (5)

[Claims] 1. In the molecule,-(AO) _n- (A is an alkylene group having 2 to 4 carbon atoms, n is an AO fraction in the molecule of 10 to 10.
80%, n n A may be the same or different) or a synthetic resin comprising an anionic surfactant having at least one selected from an aromatic ring and an anionic group. Lubricant. Wherein the anionic group ^{_{is, -SO 3 -, -SO 4 -}} , -
COO ^- for synthetic resin lubricant according to claim 1, wherein a group selected from. 3. The counter ion of the anionic group is Li, Na,
The synthetic resin lubricant according to claim 1 or 2, which is selected from K, Ca, Mg, Al and Zn. 4. A synthetic resin composition containing a synthetic resin and the lubricant according to claim 1. 5. The synthetic resin composition according to claim 4, wherein the synthetic resin is an amorphous polyester resin.