JP2001181488A - Resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in outward appearance and gloss without impairing flame retardancy, heat resistance and mechanical properties which are inherent in a glass-reinforced flame-retardant polyester resin, and to provide a molded product made thereof. SOLUTION: A flame retardant polyester resin composition is composed of (A) 100 pts.wt. of an aromatic polyester, (B) 0-100 pts.wt. of glass fiber, (C) 3-50 pts.wt. of a bromine-based flame-retardant, (D) 1-40 pts.wt. of an antimony compound and (E) 3-30 pts.wt. of calcium carbonate surface-treated with a higher fatty acid and having an average primary particle diameter of <=1 μm, and imparts to the glossy surface of a molded product a 60 deg. specular reflection of >=70%. A resin molded product is made of the above resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polyester resin composition which is excellent in the surface appearance and gloss of a molded article, and has excellent rigidity and heat resistance while ensuring sufficient flame retardancy. The present invention relates to a molded article obtained by molding the composition.

[0002]

2. Description of the Related Art In the field of industrial equipment and general home appliances in recent years, with the rapid progress of information and communication technology, various electric and electronic parts such as connectors, relays, flyback transformers, switches, and the like, and home appliances have been reduced in size. , Weight reduction is accelerating more and more. In the field of electric and electronic products and home appliances, resin products are used in a variety of ways, and among materials called engineering plastics, polybutylene terephthalate is represented by engineering plastics in order to meet required characteristics such as heat resistance, rigidity, and impact resistance. Aromatic polyester resins are widely used because of their excellent moldability.

[0003] Such polyester resins used in the field of electric and electronic appliances are often required to have flame retardancy stipulated in the UL94 standard as a required property, and in order to ensure the rigidity and strength of molded products. It is general to reinforce with glass fiber or the like, that is, a glass fiber reinforced flame-retardant polyester resin is frequently used in the molded article for the above-mentioned use. On the other hand, in the case of such a glass fiber reinforced flame-retardant polyester resin, V-
In order to satisfy the 0 standard, a considerable amount of a flame retardant or a flame retardant auxiliary or an inorganic filler such as talc or calcium carbonate as an inorganic material is added to enhance the flame retardancy.

Conventionally, in the case of such a compound, the flame retardancy and the mechanical properties can be maintained at a satisfactory level, but the dispersibility of the inorganic filler, the wettability of the inorganic filler with respect to the polyester polymer or the glass fiber in the compound. Due to the above-mentioned interaction, molded articles obtained from these compositions do not always have excellent surface appearance, and often pose a serious problem in products that emphasize surface aesthetics. In relation to this background, as a technique of blending an inorganic filler and improving mechanical properties and appearance, a polyolefin is subjected to surface treatment with a higher fatty acid and a higher fatty acid ester, and calcium carbonate having a specific average particle diameter is obtained. A technique in which a specific amount is added (Japanese Patent Publication No. 3-16979) or a method in which calcium carbonate is blended with a liquid crystal polymer so that the particle size is 2 to 1
Japanese Patent Application Laid-Open No. 4-4252 discloses a device having a thickness of 0 μm. However, none of these are applied to polyester-based resins, and in the examples, they are not glass fiber reinforced and are nonflammable.

[0005]

SUMMARY OF THE INVENTION In view of the above-mentioned state of the art, it is an object of the present invention to provide a glass-reinforced flame-retardant polyester resin which has excellent appearance and gloss, and which has inherent heat resistance and mechanical properties inherent in the polyester resin. An object of the present invention is to provide a resin composition that does not impair. Another object of the present invention is to provide a molded article represented by the resin composition in the fields of electric and electronic appliances and home appliances.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have developed a glass-reinforced flame-retardant polyester obtained by blending an aromatic polyester resin with a brominated flame retardant, an antimony compound, and glass fiber. By adding a specific amount of calcium carbonate with a specific average particle size subjected to a specific surface treatment, excellent appearance and gloss,
Flame retardancy inherent in glass-reinforced flame-retardant polyester resin,
A resin composition without impairing heat resistance and mechanical properties could be obtained, and the present invention was reached.

That is, according to the present invention, an average primary resin surface-treated with 100 parts by weight of an aromatic polyester (A), 3 to 50 parts by weight of a brominated flame retardant (C), 1 to 40 parts by weight of an antimony compound (D) and a higher fatty acid is used. A resin composition comprising 3 to 30 parts by weight of calcium carbonate (E) having a particle diameter of 1 μm or less, and a molded article comprising the same. The molded article is a molded article having a glossy surface having a 60 ° specular gloss of 80% or more. is there. Hereinafter, the present invention will be described in detail.

[Aromatic Polyester] The aromatic polyester of the component (A) used in the present invention comprises an aromatic dicarboxylic acid component and a diol component. Terephthalic acid is preferred as the aromatic dicarboxylic acid component. Examples of the diol component include alkylene glycols such as ethylene glycol, tetramethylene glycol, and propylene glycol. The aromatic dicarboxylic acid component can be derived from an aromatic dicarboxylic acid or an ester-forming derivative thereof. The diol component can be derived from a diol or an ester-forming derivative thereof.

As the aromatic polyester, polyethylene terephthalate and polybutylene terephthalate are preferred, and polybutylene terephthalate is particularly preferred.

The aromatic polyester may be one in which a part of the dicarboxylic acid component and / or the diol component is replaced by a copolymer component. Such copolymerization components include, for example, isophthalic acid, phthalic acid; tetrabromophthalic acid,
Halogen-substituted phthalic acid such as tetrabromoterephthalic acid; alkyl-substituted phthalic acid such as methyl isophthalic acid; naphthalene such as 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid Dicarboxylic acids; diphenyldicarboxylic acids such as 4,4'-diphenyldicarboxylic acid and 3,4'-diphenyldicarboxylic acid; aromatic dicarboxylic acids such as 4,4'-diphenoxyethanedicarboxylic acid; succinic acid, adipic acid; Aliphatic or alicyclic dicarboxylic acids such as sebacic acid, azelaic acid, decadicarboxylic acid, cyclohexanedicarboxylic acid, etc .; trimethylene glycol,
Aliphatic or alicyclic diols such as tetramethylene glycol, hexamethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, etc .; dihydroxybenzenes such as hydroquinone, resorcin; 2,2′-bis (hydroxyphenyl) propane ,
Bisphenols such as 2,2'-bis (4-hydroxyphenyl) -sulfone; aromatic diols such as ether diols obtained from bisphenols and glycols such as ethylene glycol; polyoxy acids such as polyoxytetramethylene glycol Alkylene glycols; oxycarboxylic acids such as ε-oxycaproic acid hydroxybenzoic acid, hydroxyethoxybenzoic acid and the like.

One or more of these copolymer components can be used. When the copolymerization component is copolymerized,
The ratio is preferably 2 per total dicarboxylic acid component (half of oxycarboxylic acid is calculated as carboxylic acid).
0 mol% or less, more preferably 10 mol% or less.

The aromatic polyester may be a branched component, for example, an acid having an ability to form a tetrafunctional ester such as trifunctional or pyromellitic acid such as tricarballylic acid, trimellitic acid or trimellitic acid, or glycerin, trimethylolpropane or pentane. An alcohol having an ability to form a trifunctional or tetrafunctional ester such as erythritol is used in an amount of 1.0 mol% or less, preferably 0.5 mol% or less, more preferably 0.3 mol% or less, based on all dicarboxylic acid components. It may be polymerized.

The aromatic polyester can be used alone or in combination of two or more.

[Glass Fiber] The glass fiber of the component (B) used in the present invention is not particularly limited as long as it is generally used for reinforcing a resin. For example, it can be selected from long fiber type (glass roving), short fiber chopped strand, milled fiber and the like.

The fibrous reinforcing material such as glass fiber is treated with a sizing agent (eg, polyvinyl acetate, polyester sizing agent, etc.), a coupling agent (eg, silane compound, borane compound, titanium compound, etc.), and other surface treatment agents. It may be.

Usually, the long fiber type glass fiber is used after being cut into a desired length before or after blending with a resin. This use mode is also useful in the present invention.

The amount of the glass fiber is preferably from 10 to 100 parts by weight based on 100 parts by weight of the aromatic polyester (A).
Parts by weight, more preferably 30 to 70 parts by weight. 1
If the amount exceeds 00 parts by weight, the fluidity of the composition in the molten state becomes extremely poor, so that a molded article having good appearance cannot be obtained, and the strength also reaches saturation, which is not preferable.

When glass fiber is used, it is preferable to use a glass fiber having a main part in the composition having a length of 0.2 mm or more because of excellent mechanical properties.

[Brominated Flame Retardant] As the brominated flame retardant of the component (C) used in the present invention, those generally used as a flame retardant can be used.

Specific examples of the brominated flame retardant include:
For example, polycarbonate produced from brominated bisphenol-A as a raw material, brominated bisphenol A type epoxy, brominated polystyrene, brominated polyacrylate, brominated polyphenylene ether, brominated biphenyl ether, brominated diphthalimide compound and the like are typical examples. Can be exemplified. Among these, the flame retardancy of polyester resin composition, flow characteristics, as those excellent in mechanical properties,
Brominated polycarbonate and brominated bisphenol A type epoxy are preferred. The brominated polycarbonate and the brominated bisphenol A type epoxy may be used alone or in combination at an arbitrary mixing ratio. That is, 100/0 to 0/1
It can be used in a mixing ratio of 00% by weight. In order to improve the fluidity and melt stability of the resin composition, it is particularly preferable that the blend ratio of brominated polycarbonate / brominated bisphenol A type epoxy is 90/10 to 50/50% by weight. The total amount of brominated flame retardant is
3 to 50 per 100 parts by weight of the aromatic polyester (A)
Parts by weight, preferably 10 to 35 parts by weight.

The amount of the flame retardant can be relatively reduced by separately adding a large amount of the inorganic filler or by adding (D) a flame retardant aid and (E) calcium carbonate described below. At least 3 parts by weight are required to achieve the object of the present invention. If the amount is less than 3 parts by weight, the resulting composition has insufficient flame retardancy. If the amount is less than 3 parts by weight, the thickness does not reach the vertical combustion standard UL94 V-0 with a thickness of 1.6 mm. If the amount exceeds 50 parts by weight, the ratio of the brominated flame retardant to the aromatic polyester resin becomes too large, and the mechanical properties, flow properties, and thermal properties originally possessed by the aromatic polyester are impaired.

[Antimony Compound] The antimony compound of the component (D) used in the present invention is blended as a flame retardant aid of the flame retardant polyester resin composition. Examples of suitable antimony compounds include Sb ₂ O ₃ and xNa ₂ O.Sb ₂ O
₅ · yH ₂ O (x = 0 to 1, y = 0 to 4). The particle size of the antimony compound is preferably from 0.02 to 5 μm. If desired, those surface-treated with an epoxy compound, a silane compound, an isocyanate compound, a titanate compound or the like can be used. Two or more antimony compounds can be used in combination.

The compounding amount of the antimony compound is 1 to 40 parts by weight per 100 parts by weight of the aromatic polyester (A). In order to effectively impart flame retardancy, it is preferable to mix the brominated polycarbonate in an amount of 20 to 70% by weight based on 100% by weight. If the amount exceeds 40 parts by weight with respect to 100 parts by weight of the aromatic polyester, the decomposition of the resin and the compounding agent is promoted, and the properties of the molded article may be deteriorated.

[Calcium Carbonate] The calcium carbonate (E) used in the flame-retardant polyester resin composition of the present invention is a calcium carbonate surface-treated with a higher fatty acid and having an average primary particle diameter of 1 μm or less. Although there are various types of calcium carbonate, heavy calcium carbonate, synthetic calcium carbonate and the like can be used, and synthetic calcium carbonate is preferable. The surface treatment of calcium carbonate is based on higher fatty acids.
Preferably, a saturated or unsaturated fatty acid of 12 to 22 can be preferably used. Specific examples of such a higher fatty acid include oleic acid, capric acid, lauric acid, palmitic acid, stearic acid, montanic acid, and kalein. Acids, linoleic acid, rosin acid, linolenic acid, undecanoic acid and undecenoic acid can be mentioned. Known methods such as a spray method and a wet method can be used for the surface treatment of calcium carbonate. The higher fatty acid is preferably 1-5% by weight of calcium carbonate, more preferably 2-3% by weight.
% By weight.

The amount of calcium carbonate added is 3 to 30 parts by weight, preferably 4 to 10 parts by weight, per 100 parts by weight of the aromatic polyester (A). If the added amount is less than 3 parts by weight, the flame retardancy is reduced. If the amount exceeds 30 parts by weight, the mechanical properties deteriorate.

[Fluorine Compound] The flame retardant polyester resin composition of the present invention may contain a fluorine compound (F). Examples of the fluorine compound include a fluorine-substituted polyolefin resin, and polytetrafluoroethylene is preferable. When a fluorine compound is compounded, the compounding amount is preferably 0.1 to 4 parts by weight based on 100 parts by weight of the aromatic polyester (A). Addition of more than 4 parts by weight is not preferred because the effect of further improving the appearance of the molded article accompanying the effect of reducing the flame retardant cannot be obtained.

[Phosphorus Compound] The flame-retardant polyester resin composition of the present invention may contain a phosphorus compound (G). Examples of the phosphorus compound include phosphoric acid, a phosphoric acid ester, a phosphite, and metal salts of phosphoric acid and phosphorous acid. Specifically, phosphoric acid; phosphate esters such as trimethyl phosphate, methyl diethyl phosphate, triethyl phosphate, isopropyl phosphate, tributyl phosphate, triphenyl phosphate, tribenzyl phosphate, and tricyclohexyl phosphate; Phosphites such as trimethyl phosphite, triethyl phosphite, tributyl phosphite, tri (δ-hydroxybutyl) phosphite, and triphenyl phosphite; monosodium phosphate, disodium phosphate,
Metal salts of phosphoric acid such as trisodium phosphate monopotassium phosphate, monolithium phosphate, aluminum phosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, hydrates thereof, and metal phosphite salts. Can be. One of these phosphorus compounds may be used alone, or two or more thereof may be used in combination.

When the phosphorus compound is blended, the amount is preferably 0.1 to 4 parts by weight, more preferably 0.2 to 1 part by weight, based on 100 parts by weight of the aromatic polyester (A). If the amount is less than 0.1 part by weight, the effect of stabilizing the molten metal and the effect of suppressing discoloration are small and the effect of stabilizing the appearance of the molded product is also small. Addition of more than 4 parts by weight is not preferable because a further stabilizing effect upon melting, a discoloration suppressing effect, and a stabilizing effect on the appearance of a molded product cannot be obtained.

[Additives] The flame-retardant polyester resin composition of the present invention may contain an antioxidant such as a hindered phenol compound or a sulfurized compound. When these components are blended, the flame retardancy is expected to be further improved.

The flame-retardant polyester resin composition of the present invention contains asbestos, carbon fiber, aromatic polyamide fiber, potassium titanate fiber, steel fiber, ceramic fiber, Polon whisker fiber and the like as long as the original properties are not impaired. Fibrous materials such as mica, silica, talc, glass beads, glass flakes, clay, wollastonite and the like, and inorganic fillers in the form of powder, powder or plate.

The flame-retardant polyester resin composition of the present invention may contain other additives. Examples of the additive include an ultraviolet absorber, carbon black, a colorant, and an antistatic agent.

[Molded Article] The present invention is also a molded article obtained by molding the above resin composition part, and this molded article can have a glossy surface having a 60 ° specular gloss of 80% or more.
That is, the resin composition of the present invention can form a glossy surface having a 60-degree specular glossiness of 80% or more by forming a molded product.

The glossiness of the glossy surface of the molded product is measured according to JIS.
This is a value measured according to the specular gloss measurement method specified in Method 3 (60-degree specular gloss) of Z8741. The molded article to be subjected to the measurement is a mirror-finished mold and has a smooth surface. [Production method] The flame-retardant polyester resin composition of the present invention is known. The method can be used. Arbitrary methods can be used for compounding each component. For example, all or part of the blended components are heated or extruded into a single-screw, twin-screw extruder or the like, and the molten resin extruded into a wire after being homogenized by melt-kneading is solidified by cooling. Next, there is a method of cutting into a desired length and granulating, but a method using another blender such as a blender, a kneader, a roll and the like may be used. In addition, a method of sequentially adding the components by using these in combination or repeating a plurality of times can be used.

In order to obtain a resin molded product from the molding resin composition thus produced, the resin composition is usually supplied to a molding machine such as an injection molding machine while keeping it sufficiently dried. Molding. It is also possible to dry blend the constituent materials of the composition, directly charge them into a molding machine hopper and melt-knead them in the molding machine.

The flame-retardant polyester resin composition of the present invention can be molded by a known method, for example, into a molded article by injection molding. The flame-retardant polyester resin composition of the present invention can provide a molded article excellent in appearance and gloss, rigidity and heat resistance while maintaining sufficient flame retardancy.

[0036]

The present invention will be described below in detail with reference to examples. In addition, the measurement of various characteristics in an Example was based on the following method.

(1) Evaluation of Appearance The molded product for evaluation is a flat plate having a width of 43 mm, a length of 80 mm, and a thickness of 2 mm, a film gate having a width of 43 mm, a mirror-finished surface of the molded product, and a back surface of a molded product. Molding was performed using a matte finish mold. The former was evaluated as a glossy surface appearance, and the latter was evaluated as a matte surface appearance. The molding machine used was Nissei Plastic Industry Co., Ltd. PS40E. The molding conditions were as follows: cylinder temperature 260 ° C, mold temperature 4
At 0 ° C., the injection pressure was 800 kg / cm ² , the holding pressure was 600 kg / cm ² , the injection speed was 50%, the injection time was 8 seconds, the cooling time was 13 seconds, the intermediate time was 1 second, and the screw rotation speed was 100 rpm. The following items were evaluated for molded articles obtained under these conditions. A. Appearance of glossy surface The surface with less unevenness and gloss was evaluated as ○, and the one with glass fiber surface floating, rough or uneven, and less glossy was evaluated as Δ. B. Matte matte appearance External appearance was evaluated as 外 観 when the surface was less uneven and glossy, and evaluated as △ when the glass fiber surface floated, was rough or uneven, and was not glossy. C. Glossy surface glossiness A. Using a digital gloss meter GM-3D manufactured by Murakami Color Research Laboratory Co., Ltd.
S: Measured according to the specular gloss measurement method specified in Method 3 of Z8741 (60 ° specular gloss).

(2) Flammability The method specified by the United States Underwriters Laboratory (U
L94) and evaluated for vertical flammability (test specimen thickness: 0.
66 mm). The test molded article was molded by the same molding machine used in the above (2) at a cylinder temperature of 260 ° C., a mold temperature of 80 ° C., and a cycle time of 30 seconds.

(3) Mechanical Properties Tensile properties (tensile strength, tensile elongation) were evaluated in accordance with ASTM D638. B. Flexural properties (flexural strength, flexural modulus) were evaluated in accordance with ASTM D790. C. Impact strength Evaluated according to ASTM D256. The test molded article was molded using a Toshiba IS60B molding machine at a cylinder temperature of 250 ° C., a mold temperature of 80 ° C., and a cycle time of 30 seconds.

(4) Melt flow rate (MFR) According to JIS K7210, temperature 250 ° C., retention 6
And a load of 2160 gf. The preliminary drying of the pellets was performed at 130 ° C. for 5 hours. The following materials were used as components constituting the compositions and molded articles in the examples.

[Polybutylene terephthalate] Polybutylene terephthalate having an intrinsic viscosity of 0.78, manufactured by Teijin Limited. [Glass fiber] Chopped strand having an average fiber diameter of 13 µm and a cut length of 3 mm. [Brominated polycarbonate] A brominated polycarbonate having brominated bisphenol A as a carbonate unit, an average number of carbonate repeating units of 5, and a terminal blocked with a 4-t-butylphenyl group. [Brominated epoxy] The average epoxy equivalent is 5400 g /
eq is a tetrabromobisphenol-type epoxy compound. [Antimony compound] Antimony trioxide [Talc] Talc powder having an average particle diameter of 8 µm. [Calcium carbonate] Calcium carbonate (A): fatty acid (oleic acid 40 to 50% by weight, stearic acid 20% by weight and palmitic acid 20)
Synthetic calcium carbonate (containing 2.5% by weight of higher fatty acid) having an average primary particle size of 0.15 μm and surface-treated with a higher fatty acid containing 2.5% by weight of higher fatty acid. Calcium carbonate (B): calcium carbonate having an average primary particle size of 2.5 μm without surface treatment. Calcium carbonate (C): Heavy calcium carbonate having no surface treatment and having an average primary particle diameter of 0.7 μm [phosphorus compound] sodium dihydrogen phosphate dihydrate (special grade reagent manufactured by Yoneyama Chemical Co., Ltd.). [Polytetrafluoroethylene] Fluon CD076 manufactured by Asahi ICI Fluoropolymers Co., Ltd.

Examples 1 and 2 and Comparative Examples 1 to 5
The materials were weighed so as to have the composition shown in Table 1 and uniformly mixed with a V-type blender to obtain a mixture. The obtained mixture was fed into a twin-screw co-extruder having a screw diameter of 44 mm (two-cut vented type,
Screw L / d = 30/1).
The operating conditions are as follows: 260 ° C. barrel, 1 screw rotation
It was 50 rpm, and the vent was evacuated to remove volatiles during extrusion. The molten resin discharged from the extruder was cooled and cut to obtain composition pellets. The pellets were subjected to the various evaluations described above as evaluation materials. Table 1 shows the evaluation results.

[0043]

[Table 1]

In Examples 1 and 2, the appearance of the molded product was good, the glossiness was high at 80 or higher, and the UL94 flammability was good in mechanical properties and fluidity in general, while having the V-0 standard. .

Comparative Examples 1, 2 and 3 were obtained by replacing the calcium carbonate used in Example 1 with another one.
Although the mechanical properties were excellent, the appearance of the molded product was inferior.

In Comparative Example 4, calcium carbonate was removed from Example 1, and although the appearance was good and the mechanical properties were excellent, the UL94 flammability was V-2 and the flame retardancy was reduced.

In Comparative Example 5, the amount of the flame retardant was increased to improve the flame retardancy of Comparative Example 4, and the UL94 flammability was V-0.
However, the appearance of the molded article was lowered, and the mechanical properties were also slightly lowered.

[0048]

According to the present invention, a polyester resin composition having excellent surface appearance and gloss of a molded article, excellent mechanical properties, and high flame retardancy, and a resin obtained by molding the composition A molded article can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/52 C08K 5/52 7/14 7/14 9/04 9/04 // (C08L 67/02 (C08L 67/02 69:00 69:00 63:00 63:00 27:18) 27:18) F term (reference) 4F071 AA27 AA42 AA43 AA50 AB18 AB21 AB25 AB28 AC15 AD01 AE05 AE07 AE17 AF14 AF32Y AF44 BB05 4J002 BD15Y CD12X CF041 CG03X DE127 DE238 DH029 DL006 EW049 FA046 FB238 FD13X GQ00

Claims (5)

[Claims] 1. An average primary particle diameter of 1 μm which is surface-treated with 100 parts by weight of an aromatic polyester (A), 3 to 50 parts by weight of a brominated flame retardant (C), 1 to 40 parts by weight of an antimony compound (D) and a higher fatty acid. The following calcium carbonate (E) 3
A resin composition consisting of up to 30 parts by weight. 2. The resin composition according to claim 1, comprising 10 to 100 parts by weight of glass fiber (B) per 100 parts by weight of aromatic polyester (A). 3. An aromatic polyester (A) containing 0.1 to 4 parts by weight of a fluorine compound (F) and / or 0.1 to 4 parts by weight of a phosphorus compound (G) per 100 parts by weight of an aromatic polyester (A). Or the resin composition according to 2. 4. The brominated flame retardant (C) is a brominated polycarbonate (a) and / or a brominated epoxy (b), and the compounding ratio (a) / (b) of both is 100/0 to 0 /. 1
The resin composition according to any one of claims 1 to 3, wherein the content is 00% by weight. 5. A molded article comprising the resin composition according to claim 1 and having a glossy surface having a 60 ° specular gloss of 80% or more.