JPS62178340A - Surface-hardened film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides surface hardness suitable for sheet keyboards, leader tapes, displays, and overlay materials with excellent scratch resistance, wear resistance, antistatic properties, and friction resistance. This relates to film.

[Conventional technology]

Conventionally, acrylic resin coating films, silane coupling agent coating films, and the like have been known as surface hardening films.

[Problem that the invention seeks to solve]

However, although these hardened films have excellent abrasion resistance and surface hardness of the coating layer, they have drawbacks such as insufficient adhesion to the substrate even with an undercoat layer, and lack of antistatic properties. was there.

It is an object of the present invention to provide a film which does not have the above-mentioned drawbacks, that is, a film having a protective layer and a hardened surface layer with anti-foaming properties that adheres well to the substrate.

[Means for solving problems]

The protective layer of the Omotesukesen/Date film of the present invention includes a compound 't&(a) containing an epoxy group and a silanol in the molecule, and a compound Q-(
bl, epoxy compound (c) at least 2fIl-curing consisting of a selected mixture +! Mixing ratio (B/A) of 1' component and KR amorphous layered silicate (Bl) 1/1
The base plastic film in the present invention may be a single film, a IllVt combination, or a continuous plastic film, whether stretched or unstretched. However, typical examples include polyolefin film, polystyrene film, polyester film, polycarbonate film, triacetyl cellulose film, cellophane film, polyamide film, polyimide film, polyphenylene sulfide film, polyetherimide film, polyether sulfone film, and polysulfone film. , polyacrylonitrile film, polyvinyl acetate film, polyether ether ketone film, and other known plastic films. Among these, single polyester or polyester composite films (films stretched to 100%) are particularly suitable because of their small thermal dimensional change and high rigidity.

The thickness of the plastic film is not particularly limited, but it is usually 0.5 μm or more and 500 μm or less, and particularly preferably 2 μm or more and 250 μm or less from the viewpoint of coating properties.

When using a composite film, the number of layers or the method is not particularly limited, but it is usually stretched by a composite extrusion method, an extrusion lamination method on a base film, or a lamination method using Yuzu adhesive. If necessary, it will be combined regardless of whether it is stretched or not.

The essence of the present invention is to use a swellable inorganic layered silicate as a component of the retention I11 layer. Here, the term "swellable" refers to an inorganic layered silicate that has the property of "swelling" by coordinating water between the eyebrows, and in the coating layer of the coating film of the present invention, this swelling property is utilized to at least Its essence is that it exists in the form of fine particles formed by partial interlayer separation.

Structurally, the swellable inorganic layered silicate used in the present invention is a phyllosilicate in which the ratio of St to 0 of the 5i04 tetrahedron is theoretically 2:5, and the crystal unit cell is oriented in the crystalline direction. It has a reversed crystal structure, and a typical example thereof can be expressed as a chemical formula as follows.

W113~L, S Xts~3.2 (S i 3.5
~4.110 + o) Z h to z, z where W: sb is an ion between N, one or more cationic ions X: ion at an octahedral position, Mg2+ or Mg2+
An ion in which a part of is replaced with at least one ion selected from the group consisting of Li", Fe", Ni", Mn", AI"+ and F3+, O: oxygen z: F"" or OH- □ Similarly, in the present invention, Si'+ at the above-mentioned tetrahedral position is Ge4+
Alternatively, some of these may be replaced with A13+, Fe3+, B3+, etc., and the swellable inorganic layered silicate referred to in the present invention also includes these.

Specific examples of these include clay threads and mica-based minerals such as natural products such as montmorillonite and vermiculite, and synthetic products such as tetrasilisic mica, taeniolite, and hectorite, which are synthesized by melting or hydrothermally and having the above general formula. be.

Among these, synthetic materials are particularly preferred because they contain fewer impurities and have a uniform composition, resulting in uniform crystals.
From the point of view of large crystal size, WX-11-X+111Mg 2.8-X-3,2-z
L'z (813,5~4.00 s o )
F1. s~2. .

or WX-(Ll-X+(LI Mg2.8-x-3,2-
xL i X (S i 3.5-4.00 io)
(OR) 1. s ~ (however, x-0,8~1.2) is preferable, and as the interlayer ion W, 1f
It is not particularly limited as long as it is a cationic ion with a tk or higher, but it is 40% or more, preferably 60% of all intercostal ions.
Above, more preferably 85% or more is Li", hydrogen or an alkyl group having 1 to 50 carbon atoms). In particular, R, -NH," (wherein R1 is an alkyl group having 6 or less carbon atoms) is suitable. Li", especially Rt NHs and Li
Coexisting yarns with + are preferable because they have good passability.

Swellable inorganic layered silicon used in the present invention! i!
i! The grain size is not particularly limited, but the average particle diameter measured by a sedimentation method is 0.05 μm to 15 μm, preferably 01 μm to 8 μm.

More preferably, the thickness is between 0.15 μm and 3 μm, since a uniform layer can be obtained. Also, 4o50% of the total particles, preferably 80cm, preferably 9cm in length
It is preferable that the surface of the coating layer is 11800A or less, preferably 400A or less, and more preferably 1008 or less, since the surface of the coating layer becomes smooth. For information on how to make such stored noodles, see %IjA 1986-9
No. 7557 specification 1. has been shamed.

In the present invention, the other component of the retention layer is a cured thread containing an epoxy group and a silicon atom (hereinafter referred to as silicon compound).
) is used.

Among silicon compounds, 41 compounds containing epoxy groups and silanol and/or siloxane in the molecule are defined by the general formula % (or aryl, n is 2 or 3, a is θ ~ 2, b is 1
~6) □ Specific representative examples include γ-crisitoxypropylalkyldialkoxysilane, γ-crisitoxypropylalkyldialkoxysilane, β(3,4-epoxycyclohexyl)ethyltrialkoxy Examples include silane-hydrolyzed steel products.

Compounds containing silanol and/or siloxane groups refer to hydrolysates of 4-alkoxy silicon and
ttct~6 alkyl, halogen, vinyl, aryl, methacryloxy, mercapto, amino, HxN-(
CHz) b-Nu- group, R1 is C1-6 alkyl or aryl, nne2 or 3. b is a compound represented by 1 to 6).

Specific examples include methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, n-
butyl silicate, 8ee-butyl silicate, ter
t-butyl silicate, methyltrialkoxysilane,
Vinyltrialkoxysilane, vinyltriacetoxysilane, vinyltrialkoxyalkoxysilane, phenyltrialkoxysilane, methacryloxypropyltrialkoxysilane, chloropropyltrialkoxysilane, alkyltriacyo-t-disilane, γ-aminopropyltrialkoxysilane , N-β (amino nibble)
γ-aminopropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, dialkyldialkoxysilane, alkylphenyldialkoxysilane,
Examples include hydrolyzates of diphenyldialkoxysilane, N-β(amineethyl)γ-aminopropylmethyldialkoxysilane, and alkyltrichlorosilane.

Hydrolysis of these silicon compounds is produced by adding and pressing a water solution such as hydrochloric acid or sulfuric acid with your fingers. It is carried out by adding gradually.During hydrolysis, alcohol, alkoxy alcohol, and various carboxylic acids such as acetic acid are produced, so hydrolysis can be carried out without dissolution. Alternatively, it is also possible to mix a silicon compound and then hydrolyze it.Usually, the resulting hydrolyzate
The solution is used as it is, but depending on the purpose, it is also possible to perform hydrocatalysis with a non-reactive medium and remove the resulting alcohol etc. by heating and/or under pressure. It is also possible to effectively replace the solvent by adding a suitable solvent to it. As the solvent, alcohols, esters, ethers, ketones, hydrocarbons, or aromatic solvents such as toluene can be used depending on the purpose, and mixed solvents can also be used if necessary. can.

In the case of 2 seconds or more, the hydrolysis may be carried out separately and mixed, or two or more kinds may be mixed and hydrolyzed after fc.

Epoxy compounds are widely used for paints, casting, etc., such as polyolefin epoxy resins synthesized by peroxidation method, polyglycidyl obtained from cyclopentadiene oxide or hexahydrophthalic acid and epichlorohydrin. Esters, polyhydric phenols such as bisphenol A, catechol, and resorcinol, or polyhydric alcohols such as (poly)ethylene glycol, (poly)propylene glycol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, siglycerol, and sorbitol. Polyglycidyl esters obtained from epichlorohydrin, cyclic epoxy resins, epoxidized vegetable oils, novolac type phenolic resins and epoxy novolacs obtained from epichlorohydrin, epoxy resins obtained from phenolphthalein and epichlorohydrin, and tomethyl chrycidyl methacrylate. Examples include acrylate monomers such as methacrylate or copolymers with styrene and the like. These silicon compounds are usually mixed with a curing agent and/or a curing catalyst. As the curing agent (curing side @), for example, specific carboxylic acid,
Alkali metal salts of nitrous acid, nitrous acid, aluminic acid, carbonic acid and thiocyanic acid, metal salts of octylic acid and naphthenic acid, organic amino acids, tin compounds, boron heptadide, zinc borofluoride, borofluoride Chemical tin.

Examples include tetramethylammonium hydroxide, tetran-butylphosphonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, aluminum chelate compounds, various epoxy curing agents, etc. Mix these for 2 seconds or more and use. It is also possible.

In particular, an aluminum compound having the following structure is extremely effective in achieving the object of the invention. The compound is fitted with At-Y
m-2c3-m) [However, Y is 0L (L ke C1-6(')7 ruki, a-
), 2 is at least one ligand derived from a compound represented by the general formula %1 (both M3 and M4 are C1-6 alkyl), and m is 3P8 of 0-3. ] This is a compound represented by Specific examples of this compound include various compounds, including composition, solubility in materials, stability, and effectiveness as a curing catalyst! J! Preferred from the viewpoint of strength are aluminum 1so-propoxide, aluminum ethoxide,
Aluminum tert-butoxide, aluminum acetylacetonate, aluminum, bis-ethylacetoacetate-mono-acetylacetonate, aluminum-di-n-butoxide-monoethylacetoacetate, aluminum-di-1so-7'lopoxide monomethylacetate acetate, aluminum glee
-butoxide-mono-ethyl acetoacetate, aluminum-dimethoxide mono-methyl acetoacetate, etc. Kohara and others are 2 to 4! It is also possible to mix and use the curing agent, and the amount of the curing agent added is 0.00% per silicon compound type 1.
0001 to 0.5i [Preferably 0.00 to
0.05 to 0.23 ft part is appropriate; less than this will result in insufficient H[1- conversion, while more than this will cause defects such as a decrease in transparency of the coating or coating resin, and a decrease in water resistance. arise.

In the present invention, the weight mixing ratio (B/A) of the silica sand forming component (A) and the swollen inorganic layered silicate (B) is set to 1/1.
It is necessary to set it to 000-2/1. This is 1/1
This is because when it is smaller than 000, sufficient adhesive strength is not exhibited without an undercoat, and there is also little effect on preventing damage. On the other hand, when the amount is more than 2/1, it is preferably strong because although it adheres well to the base material, inter-boning is likely to occur inside the coating layer, resulting in poor durability.

When forming the protective layer, other components may be used in combination as appropriate within a range that does not impair its properties. In this case, the essential components of the present invention are usually present in an amount of 60% by weight or more, preferably 80% by weight or more, and more preferably 90% by weight or more. For example, it is also possible to use a surfactant to improve the flow during coating and the smoothness of the coating film.

Furthermore, if necessary, curing catalysts, additives (e.g., mold release improvers such as silicone oil, adhesion promoters, pH
Conditioners, plasticizers, stabilizers, antioxidants, ultraviolet string absorbers, adhesives, antifoaming agents, colorants, etc.) may be used in combination.

The surface hardening layer in the present invention is coated on one or both sides of the plastic film, either entirely, in stripes, or partially.

In addition, the thickness of the surface hardening layer is particularly limited, but is usually 0.
．． The range is 0.01 to 20 pm, preferably 0.1 to 8 μm, and more preferably 1 to 4 μm.

The surface hardened film in the present invention only needs to have a hardened surface, and there is no particular limitation on the hardness, but the surface hardness according to Empi hardness (JIS K 5400) is 2H.
Above, more preferably 3L or above, the surface will be scratched.
0 The use of the surface hardened film described in the present invention is not particularly limited, but typical uses include surface protection materials for sheet keyboards, displays, CRT filters, leader tapes, panel decorative boards, A-diagram films, etc. , advertising display boards, etc.

Next, a typical manufacturing method of the present invention will be described, but it is not limited thereto.

Swollen g1 type inorganic layered silicic acid [(B) is dispersed in water or a water-soluble organic solvent to create a non-agglomerated state particle dispersion system, and silicon curing component (A) is combined with this in a predetermined ratio of 1. This is then applied to the surface of the base plastic film.

In the coating liquid, the swellable inorganic layered silicate utilizes its swelling property to form fine particles and is dispersed without settling. The sand body forming the coating liquid is water or a water-soluble organic solvent such as alcohol, and these may be used alone or in combination.

If necessary, the base film may be subjected to corona discharge treatment in air or other various atmospheres. Further, anchor treatment may be performed using a known anchor treatment agent such as urethane resin or epoxy resin. The above-mentioned coating liquid is applied onto one or both kTh of the base film using a known method such as gravure coating, reverse coating, or spray coating. After coating, it is usually 60~
Dry at 250°C for about 1 second to 15 minutes. The same coating layer can be formed separately and laminated later, but since the layer mainly made of layered silicate is somewhat lacking in breadth and strength, it can be coated on the direct printing base film. [Function] Since the surface-hardened film of the present invention uses a swollen monomorphic inorganic layered silicate with banding prevention properties, it is possible to mix uniformly without agglomeration, and as a result, the coating This makes it possible to greatly reduce the residual strain that acts between the layer and the base material, and improves the adhesive strength with the base material.

〔Effect of the invention〕 (1) The adhesive strength with the base material was greatly improved.

(2) Antistatic properties were exhibited.

(3) Shows slipperiness.

[Method of measuring characteristics, evaluation criteria]

In addition, the measuring method and evaluation criteria of the characteristics in the present invention are as follows.

(1) Surface resistivity: 8 at 20℃, 65cmRH atmosphere
After several hours, measurements were taken using a super megohmmeter.

(2) Perform scratch resistance steel wool test
C□sp-le wool uses +0000, 500g is 5
After rubbing 0 times, those with significant scratches were rated "x", those with slight scratches were rated "△", and those with no scratches were rated "○".

(3) Fine hardness: Measured based on JIS-5400.

(A Static friction coefficient ps: ASTM-D-1894B-
63, using a slip tester.

(5)? -714 Crab■] Peeled at 90 degrees using commercially available cellophane adhesive tape (manufactured by Chiban Co., Ltd.), and after peeling, cast foil on the cellophane tape. Adhesive strength "○" and 4 again
The case of 0% or more was defined as rXJ.

Next, let's see the fruits of this invention based on examples! ! Let me explain the first person.

Examples 1 to 4, Comparative Example 1.2 Polyethylene terephthalate 211 with a diameter of 100 μm.
A copolymerized polyester using terephthalic acid (85%) and 5-sulfondium isophthalic acid (15% by mole) as the acid components and ethylene glycol as the glycol component was placed on the stretched film with a diameter of 0.1 μm. A coated film is prepared as a base material. A protective layer having the following composition was formed on this co-polyester by S w
After drying in a sol state, coat it with a thickness of 2 μm. However, 7jE'l! JtJ It was carried out for 2 minutes in hot air at 165°C.

[Safeguard rVI agreement]

Layered silicone fit fabric (A): WMg2 Li (S
i40to) F2 However, W: CH3CH2-CH
2NH3'' (abbreviated as propylamine-TN) Silicon hardened layer (B): (3) CH3(CH2)3St(OH)3.

As shown in the table, when the amount of layered silicate is less than the range of the present invention (Comparative Example 1), the hardness of the paper part is good, but the adhesive strength is insufficient and is inappropriate. On the other hand, if the amount of layered silicate is larger than that of the present invention (Comparative Example 2), the surface hardness will be slightly lowered and the adhesive strength will be insufficient, which is not preferable. Good quality can be obtained only when it falls within the range of the present invention (Examples 1 to 4). In particular, the range of 1/400 to 1/80 (Example 2.3) is preferable because the balance between adhesive force and hardness is more suitable.

Examples 5 to 7 Under the same conditions as in Example fl11, the ratio of the silicon hardened layer components was reduced and the physical properties thereof were examined in the same manner. As shown in the table, there is a slight difference in hardness due to the different compositions, but it is clear that the films are surface hardened films with excellent adhesiveness and antistatic properties.

Example 8, Comparative Example 3.4 Under the same conditions as Example 1, the layered silicate was made into a non-expanded 11'M
I76-type silicate (Topy Industries, Daimonai) PDM-
7), Li y, Mgz% r, t y, (Si4
0to) F2 (abbreviated as Li-HT) was ignited and the physical properties were examined in the same manner. As shown in the table, when a non-swelling layered silicate is used, it is inappropriate because it shows no adhesive force at all (Comparative Example 3.4). When used, a surface-hardened film of good quality with excellent hardness and adhesive strength is obtained (Example 8).

Comparative Example 5 A polyethylene terephthalate biaxially stretched film with a cavity size of 100 μm before being coated with copolymerized polyester was similarly evaluated for quality defects. The film is unsatisfactory in terms of scratch resistance and surface hardness.

Claims (1)

[Claims] In a film having a protective layer on the surface, the protective layer is less than the compound (a) containing an epoxy group and a silanol in the molecule, the compound (b) containing a silanol and/or siloxane group, or the epoxy compound (c). Weight mixing ratio (B/A) of curable component (A) consisting of a mixture of two selected types and swellable inorganic layered silicate (B) (B/A) 1/10
1. A surface-hardened film comprising a cured product of a mixture of 0.00 to 2/1.