JP2701473B2 - Thermoplastic resin composition - Google Patents

Description

The present invention relates to a thermoplastic resin composition excellent in mechanical strength, low water absorption and coatability.

b. Conventional technology Polyamide resins represented by nylon 6, nylon 66, nylon 46, etc. have excellent mechanical, thermal and electrical properties. Widely used for such.

However, these polyamide resins have a drawback that the notched Izod impact strength is low, and there have been cases where problems occur in large molded products and parts used at low temperatures. In addition, due to the high water absorption, the polyamide resin that has absorbed water, when subjected to molding processing, contains air bubbles and causes whitening, not only the mechanical strength is significantly reduced due to water absorption, but also changes in dimensions and deformation. Problems arise. Since the polyamide resin has such a defect, its use as an engineering resin is limited, and there is a problem that the excellent properties of the polyamide resin itself cannot be utilized.

On the other hand, olefin-based resins such as polyethylene and polypropylene are inexpensive, hardly exhibit water absorption, and have good water absorption resistance, but have drawbacks in that paintability and physical properties at high temperatures are poor. Therefore, in order to supplement and improve the respective disadvantages of the polyamide resin and the olefin resin, it has been attempted to use both of them in combination. However, simply melting and kneading a polyamide resin and an olefin-based resin has poor compatibility, peels off each other, and does not have sufficient impact resistance. We attempted to compound an ethylene-propylene copolymer rubber to improve the impact resistance, but the effect of improving the impact resistance was not sufficient, the molded appearance was poor, and the peeling phenomenon was remarkable. However, they could not be used as industrial materials.

c. Problems to be Solved by the Invention The present inventors have improved the compatibility between a polyamide resin and an olefin resin in a mixture of a polyamide resin and an olefin resin, and improved the impact resistance and coating properties of the mixture. As a result of intensive studies, when blending a specific rubbery polymer with a polyamide resin and an olefin resin, an ethylene-functional group-containing monomer copolymer was added to a vinyl (co)
It has been found that a thermoplastic resin composition having unprecedented performance can be obtained by blending a multi-phase structure in which a polymer has undergone a graft reaction, and the present invention has been achieved based on such findings.

d. Means for Solving the Problems That is, the present invention relates to (a) 10 to 90% by weight of a polyamide resin, (b) 90 to 10% by weight of a polyolefin resin, and 100 parts by weight of the total of the components (a) and (b). (C) an olefin unit and a carboxyl group, an acid anhydride group,
A copolymer mainly composed of an unsaturated compound unit having at least one functional group selected from an oxazoline group and an epoxy group, and a vinyl (co) polymer composed of at least one vinyl compound grafted on the copolymer. A polymer having a phase structure and (d) an ethylene-α-olefin-based copolymer, a block copolymer composed of an aromatic vinyl compound and a conjugated diene compound, a block copolymer composed of an aromatic vinyl compound and a conjugated diene compound, or Hydride of random copolymer,
And at least one polymer selected from hydrides of conjugated diene polymers, wherein the total amount of (c) and (d) is 1 to
600 parts by weight, and (c) /
(D) A thermoplastic resin composition characterized in that the weight ratio of the component is from 1 to 90/99 to 10.

 Hereinafter, the present invention will be described in detail.

The polyamide resin used in component (a) of the present invention, represented generally by the following formula _{H 2 N- (CH 2) x} -NH 2 ( wherein, x is an integer between 4-12.) a linear diamine represented by the following formula HO ₂ C- (CH ₂₎ (wherein, y is an integer between 2~12.) y-CO ₂ H is prepared by condensation of a linear carboxylic acid represented by And those produced by ring-opening polymerization of lactams. Preferred examples of these polyamides include nylon 66, nylon 69, nylon 610,
Nylon 612, nylon 6, nylon 12, nylon 11,
Nylon 46 and the like.

Also, nylon 6/66, nylon 6/610, nylon 6/1
2, nylon 6/612, nylon 6/66/610, nylon 6/66/1
Copolyamides such as 2 can also be used.

Furthermore, semi-aromatic polyamides obtained from nylon 6 / 6T (T: terephthalic acid component), aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and metaxylene diamine or alicyclic diamine, and meta xylene diamine Examples thereof include polyamides obtained from linear carboxylic acids. The polyamide may be used alone, or two or more polyamides may be used in combination. Particularly preferred are nylon 66, nylon 6, and nylon 46.

The relative viscosity η _rel of the polyamide resin used in the present invention (9
(7% sulfuric acid concentration 1 g / 100 ml, measured at 30 ° C.) is 1 to 5, preferably 1.5 to 4.5, more preferably 2 to 4.

The olefin resin of the component (b) is preferably a polypropylene resin and / or a polyethylene resin. Examples of the polypropylene resin include a propylene homopolymer, a copolymer of propylene with ethylene and an α-olefin, and a mixture of these with a homopolymer or a copolymer of an α-olefin other than propylene.

The α-olefin used here has 6 carbon atoms.
To 12 are used, 1-hexene, 1-octene,
1-decene, 3-methyl-1-pentene, 4-methyl-
1-pentene and the like are particularly preferred. Α in the above copolymer
-The olefin content is preferably 0.5% by weight or less.

As the polyethylene resin, any one of high density, medium density or low density can be used, and a polyethylene resin modified with another monomer or a halogen compound can also be used. Particularly preferred component (b) is a polypropylene resin.

The amounts of the components (a) and (b) used are (a) component /
(B) Component: 10-90 / 90-10% by weight, preferably 20%
~ 90/80 ~ 10% by weight, more preferably 20 ~ 80/80 ~ 20,
Particularly preferably, it is 30 to 70/70 to 30% by weight.

When the amount of the component (a) used is less than 10% by weight (in the region where the amount of the component (b) used exceeds 90% by weight), the paintability is poor.
In the region where the amount of the component (a) used exceeds 90% by weight (the region where the amount of the component (b) used is less than 10% by weight), the effect of improving the water absorption is small.

The polymer (c) having a multiphase structure of the present invention is used as a compatibilizer for the components (a), (b) and (d). The component (c) is mainly composed of an olefin unit and an unsaturated compound unit having at least one functional group selected from a carboxyl group, an acid anhydride group, an oxazoline group, and an epoxy group in the multiphase structure polymer. The copolymer is, for example, a binary, ternary, or multi-component copolymer of an olefin obtained by high-pressure radical polymerization and the above unsaturated compound monomer or another unsaturated monomer. As the olefin, ethylene and propylene are preferred, and particularly preferred is ethylene. Particularly preferred among the above copolymers are binary copolymers of ethylene-maleic anhydride.

The copolymer preferably has an olefin content of 60 to 99.5% by weight, a functional group-containing unsaturated compound monomer of 0.5 to 40% by weight, and another unsaturated monomer of 0 to 39.5% by weight.

Examples of the carboxyl group-containing unsaturated compound include acrylic acid, methacrylic acid, and maleic acid.Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride and itaconic anhydride, and as the oxazoline group-containing unsaturated compound. Include oxazoline and the like, and examples of unsaturated compounds containing an epoxy group include glycidyl methacrylate and allyl glycidyl ether.

Preferred functional groups are an epoxy group and an acid anhydride group,
Particularly preferred are acid anhydride groups.

The vinyl (co) polymer in the multiphase thermoplastic resin used in the present invention specifically includes styrene, methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorostyrene, α-methylstyrene, α
-Aromatic vinyl monomers such as ethylstyrene, (meth)
Acrylic acid methyl, ethyl, propyl, isopropyl, butyl, 2-ethylhexyl, cyclohexyl, dodecyl, esters such as octadecyl, vinyl methyl ethers, vinyl ethers such as vinyl ethyl ether, acrylonitrile, vinyl cyanide compounds such as methacrylonitrile and Examples include amino acrylate compounds, which are used alone or in combination of two or more.

The multi-phase thermoplastic resin referred to in the present invention is a specific functional group-containing olefin copolymer or a vinyl (co) polymer matrix in which a different component, a vinyl (co) polymer or a specific functional It means that the group-containing olefin copolymer is uniformly dispersed spherically.

The particle size of the dispersed polymer is from 0.001 to 10 μm, preferably from 0.01 to 5 μm. 0.001μ of dispersed resin particle diameter
If it is less than 10 m, or if it exceeds 10 μm, the mechanical strength of the obtained composition is undesirably reduced.

The number average degree of polymerization of the vinyl (co) polymer in the multiphase thermoplastic resin of the present invention is 5 to 10,000, preferably 10 to 5,000.
Range.

In the multi-phase thermoplastic resin of the present invention, the specific functional group-containing olefin copolymer contains 5 to 95% by weight, preferably 20% by weight.
It is preferable that the content be in the range of 90% by weight to achieve the object of the present invention.

The grafting method for producing the component (c) of the present invention may be any of the well-known methods such as chain transfer method and ionizing radiation irradiation method. This is the method described in JP-A-48856.

In the component (c) of the present invention, the amount of the vinyl (co) polymer grafted to the functional group-containing olefin copolymer, that is, the graft ratio is preferably at least 1% by weight.

The graft component is preferably an alkyl (meth) acrylate polymer, an aromatic vinyl polymer or a copolymer of an aromatic vinyl compound and a vinyl cyanide compound, and more preferably an alkyl (meth) acrylate polymer. And styrene-acrylonitrile copolymer.

Examples of the ethylene-α-olefin copolymer which is the component (d) of the present invention include ethylene-α-olefin copolymers and ethylene-α-olefin-polyene copolymers. The olefin is an unsaturated hydrocarbon compound having 3 to 20 carbon atoms, for example, propylene, butene-1, pentene-1, hexene-1, heptene-1, 4-methylbutene-1, 4-methylpentene -1 and the like, and particularly preferred is propylene. The weight ratio of ethylene to α-olefin is
95: 5 to 5:95, preferably 95: 5 to 20:80. The preferred Mooney viscosity (ML _{1 + 4} , 100 ° C.) is 5 to 200, preferably 5 to 100, from the viewpoint of impact resistance.

The block copolymer comprising either an aromatic vinyl compound and a conjugated diene compound represented by the general formula _{(A-B n, (A} -B n A, (A-B n X ( wherein, A represents an aromatic vinyl compound polymer A block, B is a conjugated diene compound polymer block, X is a residue of a coupling agent, and n is an integer of 1 or more.)

Here, the polymer block mainly composed of an aromatic vinyl compound means a conjugated diene compound block containing a conjugated diene compound alone or a conjugated diene compound containing 60% by weight or more, preferably 80% by weight or more, of a conjugated diene compound and an aromatic compound. Any structure having a so-called tapered block, which is a copolymer block with a vinyl compound and in which a vinyl aromatic compound is randomly bonded or gradually increased, may be used.

Further, examples of the polymer block mainly composed of a conjugated diene compound include those having a block in which the conjugated diene compound is bonded in a low cis type and a block in which the conjugated diene compound is bonded in a high cis type.

As the vinyl aromatic compound used here, those described above are used, but styrene is preferred.

As the conjugated diene compound, 1,3-butadiene, 2-
Methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2-cyano-1,3-butadiene, Substituted linear conjugated pentadienes, linear and side chain conjugated hexadienes, and the like. Of these, 1,3-butadiene and 2-methyl-1,3-butadiene are preferably used,
The use of 1,3-butadiene is particularly preferred.

The weight average molecular weight of the entire block copolymer is preferably 10,000 to 500,000, more preferably 20,000 to 300,000.
It is. Not only one kind of block copolymer but also a combination of different structures and different vinyl aromatic compound contents may be used. Moreover, what hydrogenated the said block copolymer can also be used as a block copolymer.

Furthermore, a hydride of a random polymer of a vinyl aromatic vinyl compound and a conjugated diene compound is also preferably used.

In the component (d) of the present invention, the hydride of the conjugated diene polymer is, for example, preferably a polybutadiene block segment (C) having a 1,2-vinyl structure of 20% or less and one of the bound butadiene portions. , 2-vinyl structure is 30 to 95
% Polybutadiene or a hydride of a block copolymer having a block segment (D) composed of an aromatic vinyl-butadiene copolymer, which has a general formula (C-D _n , (C-D _n C, (C (wherein, X is a coupling agent residue, n represents 1 or more is an integer.) -D _n X is represented by.

The hydrogenation rate of the hydride in the component (d) of the present invention is:
The olefinic unsaturated bond in the conjugated diene compound polymer is preferably at least 80% or more, more preferably 90% or more, particularly preferably 95% or more.

Preferred components (d) are ethylene-propylene-based copolymers and the above-mentioned hydrides, more preferably ethylene-propylene-based copolymers, and copolymers composed of polystyrene blocks and random copolymer blocks of styrene and butadiene. And hydrides of polymers comprising polystyrene blocks, high vinyl polybutadiene blocks and low vinyl polybutadiene blocks, and hydrides of polymers comprising low vinyl polybutadiene blocks and high vinyl polybutadiene blocks.

The component (d) of the present invention has a purpose of improving impact resistance, and is a specific one selected from rubbery polymers. There are many rubbery polymers, but those other than the component (d) of the present invention have no improvement or little improvement in impact resistance.

The total amount of the components (c) and (d) used in the present invention is (a)
1 to 600 parts by weight with respect to a total of 100 parts by weight of + (b) component,
The amount is preferably 5 to 500 parts by weight, more preferably 5 to 400 parts by weight, particularly preferably 5 to 300 parts by weight. If the amount used is less than 1 part by weight, the impact resistance is poor, and if it exceeds 600 parts by weight, the heat resistance is high. Poor performance, impact resistance and paintability.

The use ratio of the component (c) and the component (d) is such that the weight ratio of the component (c) / the component (d) is from 1 to 90/99 to 10, preferably from 5 to 80, from the viewpoint of impact resistance and paintability. / 95-20, more preferably 10-50 / 90-50% by weight, particularly preferably 10-45 / 90
~ 55% by weight.

Further, a graft polymer composed of a vinyl (co) polymer obtained from a propylene polymer or an ethylene polymer and at least one vinyl monomer may be used in combination with the compatibilizer (c). .

As the vinyl monomer used here, the above-mentioned aromatic vinyl monomer, vinyl cyanide compound, alkyl (meth) acrylate and the like are used.

In obtaining the thermoplastic resin composition of the present invention, component (c) and / or component (d) can be crosslinked by a known crosslinking method.

As the crosslinking used here, peroxide crosslinking, resin crosslinking, sulfur crosslinking, and the like used for ordinary rubber are used.

As a specific crosslinking agent, for example, a crosslinking agent, a crosslinking assistant, a crosslinking accelerator, and the like described in “Crosslinking Agent Handbook (written by Shinzo Yamashita and Tosuke Kaneko, Taiseisha)” are used.

(A), (b), (c), (d)
After the components are melt-mixed, the crosslinking agent is added, and after further kneading, a static crosslinking method of crosslinking by a hot press or the like,
There is a dynamic cross-linking method in which a cross-linking agent is added and cross-linking is performed while maintaining the melt-mixing state. The dynamic cross-linking method is preferable because of its excellent performance.

In the dynamic crosslinking method, the crosslinking agent comprises (a), (b),
All of the components (c) and (d) may be added at the same time, or an arbitrary component or a part of the components may be mixed with a crosslinking agent, and the remaining components may be added later. The whole or one part may be melt-mixed, and after adding the remaining components, a crosslinking agent may be added for crosslinking.

As a composition suitable for performing crosslinking by adding the crosslinking agent, preferred are (a) + (b) + (c) +
(A) + (b) component amount in component (d) is 50% by weight or less;
More preferably, it is 45% by weight or less.

The thermoplastic resin composition of the present invention can be obtained by kneading the above components with various extruders, a Hanbury mixer, a kneader, a roll, or the like. The order of addition of each component at the time of melt-kneading is not particularly limited, and there are a method of mixing and kneading all components, a method of kneading arbitrary components, and then adding and kneading the remaining components.

When using the thermoplastic resin composition of the present invention, various fillers can be added.

For example, glass fiber, carbon fiber, metal fiber, glass beads, asbestos, glass flake, wollastonite, calcium carbonate, talc, barium sulfate, mica,
Fillers such as potassium titanate whiskers, fluororesins, molybdenum disulfide, carbon black, and titanium oxide can be used alone or in combination.

Among these fillers, those having a fiber shape such as glass fiber and carbon fiber preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more.

These fillers can be used in an amount of 5 to 150 parts by weight based on 100 parts by weight of the composition of the present invention.

Further, known additives such as a flame retardant, an antioxidant, a foaming agent, a lubricant, a plasticizer, a pigment, and a dye can be used.

Preferred flame retardants are red phosphorus, halogen-based,
More preferred are decabrom diphenyl ether,
Brominated polystyrene, brominated polyphenylene ether,
A combination of a brominated epoxy oligomer and antimony trioxide. A preferred lubricant is montanic acid wax.

Further, other polymers depending on the required performance, for example,
ABS resin, AES resin, MBS resin, AS resin, HIPS, polystyrene, thermoplastic polyester, polycarbonate, porsulfone, polyethersulfone, polyimide, PPS,
Polyether ether ketone, vinylidene fluoride polymer, polyphenylene ether, crosslinked particles and the like can be appropriately blended.

The thermoplastic resin composition of the present invention can be used as various molded articles by injection molding, sheet extrusion, vacuum molding, heteromorphic molding, foam molding, stampable molding, and the like.

Various molded products obtained by the above molding method, exterior and interior members of automobiles, functional members, utilizing its excellent performance,
And it is used for various electrical and electronic parts, housings, etc.
Drive gears, engine rocker covers, and the like.
Various parts related to electricity and electronics, such as switches,
A connector and a coil bobbin are mentioned, and among them, those which are required to have a snap-fit property are suitably used.

e. Examples The present invention will be described in more detail by way of examples, which are all illustrative and do not limit the content of the present invention.

In the following examples, parts and% indicate parts by weight and% by weight, respectively.

(A) of the present invention used in Examples and Comparative Examples of the present invention,
The components (b), (c) and (d) are shown below.

1. Component (a) A-1 (nylon 6) η _rel obtained by ring-opening polycondensation of ε-caprolactam 2.77 (9
Nylon 6 having a concentration of 1 g / 100 ml and measured at 30 ° C.) using 7% sulfuric acid was used.

A-2 (nylon 66) Nylon 66 of η _rel 2.95 (measurement conditions are the same as A-1) obtained by polycondensation of hexamethylenediamine and adipic acid was used.

A-3 (nylon 46) Nylon 46 of η _rel 3.55 (measurement conditions were the same as A-1) obtained by polycondensation of tetramethylenediamine and adipic acid was used.

2. (b) Component B-1; manufactured by Mitsubishi Yuka Co., Ltd., polypropylene MH8 B-2; manufactured by Mitsubishi Yuka Co., Ltd., polypropylene MA3 B-3; manufactured by Nippon Petrochemical Co., Ltd., polyethylene staphrene E7913 (C) Component C-1 250 parts of distilled water and 0.25 parts of polyvinyl alcohol were added to a stainless steel autoclave, and 70 parts of an ethylene-glycidyl methacrylate copolymer (glycidyl methacrylate content: 15%) was added and dispersed with stirring. 0.15 parts of benzoyl peroxide as a radical polymerization initiator and 0.6 parts of t-butylperoxymethacryloyloxyethyl carbonate as a radical (co) polymerizable organic peroxide were dissolved and added to 21 parts of styrene and 9 parts of acrylonitrile.

The temperature was raised to 60 to 65 ° C., and the polymerization reaction was carried out for 2 hours to impregnate a vinyl monomer containing a radical polymerization initiator and a radical (co) polymerizable organic peroxide. Next, the temperature was raised to 80 to 85 ° C., and a polymerization reaction was performed for 7 hours. After washing with water and drying, a grafting precursor was obtained. The grafting precursor was extruded with an extruder (200 ° C.) and a grafting reaction was performed to obtain a multi-phase thermoplastic resin C-1. C-1 had a dispersed particle diameter of 0.3 to 0.4 [mu] m as observed by a scanning electron microscope, and the graft ratio of the styrene-based polymer to the ethylene-glycidyl methacrylate copolymer was 32%.

C-2 to C-4 C-2 to C-4 were produced under the conditions for producing C-1 while changing the functional group-containing olefin polymer or vinyl monomer species.

The dispersed particle size and the graft ratio of the dispersed phases C-2 to C-4 were almost the same as C-1.

4. Component (d) Polymer D-1 Ethylene-propylene copolymer rubber (EP912P, manufactured by Nippon Synthetic Rubber Co., Ltd.) Polymer D-2 (CDC block copolymer) Hydrogenated polybutadiene having 2-vinyl content of 10%, molecular weight of 60,000, 1,2-vinyl content of block D portion of 60% and molecular weight of 120,000 (hydrogenation rate 98%)
Was used.

Polymer D-3 (ABC block copolymer) Block A is a styrene block having a molecular weight of 40,000 (styrene content 30%), and block B is polybutadiene having a molecular weight of 80,000 and a 1,2-vinyl content. The block C was a polybutadiene having a molecular weight of 10,000 and a hydride of a block copolymer having a 1,2-vinyl content of 12% (hydrogenation rate: 98%).

Polymer D-4 (AB block copolymer) Block A is a block of styrene and block B
Used was a hydride (98% hydrogenation rate) of a block copolymer having a molecular weight of 200,000, which is a random copolymer of styrene and butadiene. The styrene content of the block A is 10% and the styrene content of the block B is 20%.

The components (a), (b), (c) and (d) were mixed in the composition ratios shown in Table 1, and kneaded with a twin-screw extruder to form pellets. After sufficiently drying the obtained pellet, a test piece for evaluation was obtained with an injection molding machine.

Impact resistance (Izod impact strength): Measured at 23 ° C. with a 1/8 ″ notch according to ASTM D256.

Heat resistance (thermal deformation temperature): 1 / thickness according to ASTM D648
4 ″, measured with a load of 4.6 kg / cm ² .

Mechanical strength (flexural strength): Measured according to ASTM D790.

Coatability: A 25 μm-thick urethane coating was performed using the following paint, curing agent, and thinner manufactured by Origin Electric Co., Ltd. A grid (100 pieces) was put on the coating film, and the number of grids to be peeled off with a cellophane tape was checked.

Coating: Origin plate ZNY Hardener: Polyhard H thinner; Origin thinner # 210 Absorbance: 1/8 "UL Bar test piece was prepared, and this test piece was
It was left in an atmosphere of 100 ° C. and 100% RH for 200 hours, and was calculated from the absolute dry weight and the water absorbed weight after molding by the following formula.

In Examples 1 to 14, the thermoplastic resin compositions having the effects intended by the present invention are obtained.

In Comparative Example 1, the amount of the component (a) used is large outside the range of the present invention (the amount of the component (b) used is small outside the range of the present invention), the water absorption is large, and the water absorption resistance is high. Inferior.

In Comparative Example 2, the amount of the component (a) used was small outside the range of the present invention (the amount of the component (b) used was large outside the range of the present invention), and the coatability was poor.

Comparative Example 3 is an example in which the component (c) was not used,
Poor impact resistance and paintability.

In Comparative Example 4, the amounts of the components (c) and (d) used were small outside the range of the present invention, and the impact resistance and the paintability were poor.

In Comparative Example 5, the component (c) had no graft, and the impact resistance and the coating property were poor.

Comparative Example 6 is an example in which the component (d) of the present invention was not used, and the impact resistance was poor.

f. Effects of the Invention The thermoplastic resin composition of the present invention is excellent in mechanical strength such as impact resistance, paintability, low water absorption and dimensional stability, and is required to have a high quality for automobile exteriors. -It provides molded products such as interior parts and various electrical and electronic parts, housings, etc., and has great industrial utility value.

Claims (1)

(57) [Claims] (1) 10 to 90% by weight of a polyamide resin; (b) 90 to 10% by weight of a polyolefin resin; , Acid anhydride group,
A copolymer mainly composed of an unsaturated compound unit having at least one functional group selected from an oxazoline group and an epoxy group, and a vinyl (co) polymer composed of at least one vinyl compound grafted on the copolymer. A polymer having a phase structure; and (d) an ethylene-α-olefin-based copolymer, a block copolymer composed of an aromatic vinyl compound and a conjugated diene compound, a block copolymer composed of an aromatic vinyl compound and a conjugated diene compound, or Hydride of random copolymer,
And at least one polymer selected from hydrides of conjugated diene polymers, wherein the total amount of (c) and (d) is 1 to
600 parts by weight, and (c) /
(D) The thermoplastic resin composition, wherein the weight ratio of the component is 1 to 90/99 to 10.