JPH02273580A - Surface treatment of porous base material - Google Patents

Abstract

PURPOSE:To prevent the generation of a pinhole by treating the surface of a porous base material with ultraviolet curable paint containing a titanocene compound as a photo-reaction initiator and curing the paint infiltrated in the porous interior of said base material. CONSTITUTION:Ultraviolet curable paint containing a titanocene compound as a photo-reaction initiator is applied to a porous base material such as a calcium silicate plate or a concrete panel to be infiltrated therein. Thereafter, the formed film is irradiated with ultraviolet rays to be dried. When the titanocene compound is used as the photo-reaction initiator as mentioned above, the paint infiltrated in the porous interior of the base material can be cured. Therefore, the generation of adhesion inferiority or bleed/pinhole can be prevented.

Description

[Detailed description of the invention]

(Industrial Application Fields) The present invention is used to strengthen porous substrates, apply paint to the surface of porous substrates, improve adhesion during lamination, and prevent bleeding. <Prior art and problems to be solved> Regarding the surface treatment method of 'l'l'l1 quality base material to prevent the occurrence of paint film defects such as bottle holes, etc. <Prior art and problems to be solved> The back side of the base material is also j.
< is surface? 1:) Internal IJ small hole, void, m groove, 'j')
The layer is a porous base material 9 with a large number of conduits and the like interposed therein. For example, paper or cloth with a rough surface may be used to make it waterproof or have physical strength, or wood boards or other materials may be used to make them waterproof, coated with a top coat, or laminated. , resin liquid, brimer paint,
There are many methods of applying, impregnating, and curing surface treatment agents such as sealers. However, conventionally known surface treatment agents usually take several minutes to several days to harden, and they have the problem of long curing times. IL″Pt, Nanokome table 1! +!: Deep hard Ihi 1 dog!; Back is often,
1. Under an insufficiently cured state. :
J5 and 10-L coating paint, laminate, etc.
- If processed, poor adhesion or bleeding will occur -1! - is 1. At 1゜I1, I used a surface treatment agent on the UV-curable room heater.
Ultraviolet ray evaporation 1;'',!: /') Several seconds - several tens of seconds 11J) A':L'') Short 1 Samurai 'C coating (jr) method has also been adopted. cK) 1w1. I'm here. 1. Therefore, the method of using ultraviolet curing is to impregnate the inside of the 15-hole base 11.4, and the paint is irradiated! The r-ultraviolet rays reach the inside of the L-substance (, 5 difficulties < 1. Also, the 1,5-in series also cause light L-energy.
The low intensity of C is popular, the depth is ii2 11, lJ<i1. Therefore, although the curing time can be shortened, the defects still remain problematic in that the vM is not eliminated. In view of the problems such as 1T-("I), the present invention, Jτ, etc., has developed a method that sufficiently cures not only the surface layer but also the deep layer even when applied to L-based substrates with many purple one-line curing paints. Supekkei, general @ side (1, Tayu prefecture, W-4, Tachi no Hiaru, 1 for the present invention)
The present invention is based on r71. A porous base material that is coated with an ultraviolet curable material containing a titanocene compound as a photoreaction initiator, impregnated with it, irradiated with ultraviolet rays, and cured the coating film. These are surface treatment methods J and Nikan I. Therefore, many of the normal photoreactions used in ultraviolet curable paints start in the deep layer inside the porous material.
．． The paint used in 5 was sufficiently cured, but unexpectedly, by using the titanocene compound, it was sufficiently cured.
, -Itiru with things. Hereinafter, the present invention will be explained in detail. 5. The ultraviolet peeling type paint used in the present invention contains an ultraviolet polymerizable vehicle and titanocene as a photoreaction initiator as essential components. It contains pigments, extender pigments, solvents, additives, etc. [1i1^1. In the bilayer component 4 min. and j~, a compound with radically polymerizable unsaturation and quaternary viscosity in the molecule can be used. Specifically, it is used in ordinary ultraviolet curable paints. De saturation, jj 17 S? resin,
I'm tired of it-r)? Riruka resin, i.: Saturated urethane resin 5, unsaturated j-bokira resin, Kofune, Japanese polygammaide resin, or - these resins and an ethylenically unsaturated group.
A typical example of this is a mixture with a reactive diluent that exhibits superior IJ' post-processability, recoatability, and excellent interlayer adhesion even under a wide range of ultraviolet irradiation conditions.
1. Bi I and Tal of 1.' are preferred because they have good heat buildup properties (quick drying properties). The main component of the human tar is 5-tan oligomer (STacrylic acid), which has J2, A''3, 5-acrylic acid, tan''-7- is the molecule (J: 5-tan oligomer). 8・
and radical polymerization ability, 1: unsaturated double, with bond ``・1'' filtration N1 ・L equal proportion)
At room temperature, tens of thousands of culms are widely found in the viscous stage1.
, For example, polyisocyanate and 6 hydroxyl groups (meth)
By reaction with a furylic acid ester (1(are/
In addition to the polyether names acrylic urethane, tan, polyurethane, sprue type acrylic urethane oligomer, polybutadiene urethane oligomer, etc. Specifically, l-ruene diisocyanate/anate, -, methane diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, -
silane diisocyanate, these isomers'')
Polyoxymethylene glycol 1-, Bo 11 Oxyethyl 1. Polyisocyanates such as isocyanate-1 and 4-terminated compounds (particularly preferred are Examples include reaction products of non-yellowing type polyisocyanate) with compounds having white monohydroxyl groups and unsaturated groups. (Meta) - "Cli1/-), Hydro4-dibutyl (Meth) Acrylic - -1), Human l-1xy", Naru (Meth)゛γCli L/-),, Glyshiji? The vehicle is composed of these acrylic urethane oligomers and a reactive diluent. Reactive diluent and 1. , r is 1Cj-tyl^xyl (meth)acrylate, 2-1-do

[ ] + diethyl (meth)acrylate, isovo) 1.・
-L (I) Acrylate, Tribrobylene Grini'-
Lusiatari 1. ．． / −), 1.6-hexanedio-ludia-acrylate-1.,? ) laethyleneglyfur difcryl),) rimethylv1-rubrovant (, meth)-acrylate, pentaerythri)・-lutetof (meth)
acrylate, ditrimethylolpropane pentaacrylate, dipentaerythritol 1, vinyl acetate, N-birubin 1] lydone, dimethyl(meth)rcrylamide, birtol T, n, divinylbenzene, etc. These reaction diluents are preferably blended in an amount of 50 to 500 parts by weight per 100 parts by weight of acrylic urethane oligomer. A titanocene compound is used as the photoreaction initiator. This titanocene compound is a compound represented by the following general formula. Formula (1) %Formula% (1) [In the formula, the two R' groups are each independently j7, 91:] pentagenyl e1 indenyl e or 4,5°6.7~
Tetrahydroindenyl e, even if unsubstituted, C8-Cl 11-'-'-alkyl or C4
~Cl11-alkoxy, Cx'' C111-alkenyl, Cs'''-C,-cycloalkyl, C6-・-C0
-aryl, C7-C+a-aralkyl, cyano or C-aryl, or two R' groups may be substituted with one or more of the following: Formula (II) unsubstituted or substituted as above [wherein, X l;! (-co-iiL (r11!
1, 2, 3; ), with 2 to 12 carbon atoms substituted or not substituted with phenyl 1
)゛T alkylidene, SiR2, or 5nR with 5 to 7 ring carbon atoms f
3(R' is C, ~(, +2-Al1-l, Cs''-CI
2-Cycloaltole, Ca- (:9.-aryl or C4~C+a]). ] Based on 1. Therefore, R' is a small <1! of the two ortho positions to the gold'$-7M elementary bond! :6tilno, one of which is substituted with fluorine,) carbocyclic ring or 5-membered or 6-membered ring
A membered heterocyclic ring T'U, 'aromatic ring -), which further contains a substituent, F) -goa-, but may be, or R
', J: R3 is connected, and the group of formula (1■) is --Q-Y --, --(III) [wherein, 0 is
A carbocyclic aromatic ring in which the 2"3 g) bond is in the 01 position relative to the Y group, and the Y group 1: !lj jy r
When the m-position is substituted with a fluorine atom f and C is 015, t9. It's okay oYi:i
, CH2, 2-12 carbon atoms -r-r-kyljn, 5-7 ring carbon atoms, 5-7 ring carbon atoms, direct bond, NR', O, SSSO. SO2, C01SII arc or -5nR3 (R' is t-
As written. ), and R3 has the same meaning as R2, or has the same meaning as R2, or has the same meaning as R2, or is not a substituted phenylalkynyl, R5, CN, or substituted phenylalkynyl, R5, CN, or substituted phenylalkynyl. i”. Or, it is SI■, and Iri7 is 1 in titanocene.
Contains one or more free esterified or esterified polyoxaalkylene groups; 1, ] titanocene, shown as: Specifically, the titanocene compound is bis(cyclopentadienyl)-bis(4-decyloxy-2,3,5
,6-titrafur(1)phenyl)titanium, bis(
cyclopentagenyl)bis(pentafluorobutenyl)-titanium, bis(cyclopentagenyl)-bisr4-(1'4',7'-)rioxaunte'yl)
-2, :). 5.6-Titrafluorophenyl]-titanium, bis(methylcyclopentagenyl)-bis[4-(1'
, 4', 7'-1-lyoxaundecyl) 2.3
゜5.6・-Tetrafluorophenyl] Nata! , um,
bis(sic■7bentazier;,ru)-bis[4-(1'
,4',? ',10'-tetra-1-zadyl)
,,, -2,3,5,6-titrafluoro[1phenyl]-titanium, bis(methylcyclobentadiT',!
)-bis[3-(1',4',7'trioxahendecyl)-2,6-difluorocarbon. -le] -+
9nium, bis(cyclopentagenyl)-bis(3
-(1',4',7',10'triAxadodecyll-2,6-)lifluorophenyl]-, titanium and bis(cyclopentagenyl)-bisr:l-(
Typical examples include 1',4'-diokiW beni/chill) ~2,6-difluorophenyl titer'~ and Udokasa. The titanocene compound is preferably 0.1 to 5 parts by weight, particularly preferably 42 to 5 parts by weight, based on 100 parts by weight of the vehicle component.
It is appropriate to mix 3 parts by weight. optionally α,α-dimethyl-α-hydroxya7tobutophenone and 17xycyclohexylacetralone;
Used in combination with common photoreaction initiators such as benzyl dimethyl ketal, α, α-dimethyl-α-morpholineaceto-p-methylthiophenone, α, α-diethyl-α-dimethylaminoaceto-p-morphumerinophenone, and acylphosphine oxide. It is also possible to do so. Coloring dye pigments and extender pigments do not necessarily need to be blended in order to strengthen the base material, but it is desirable to blend them in order to improve the smoothness of the surface of the porous base material and to add color to the base material. For the colored dyes and pigments 12, ordinary inorganic, organic, dyes and pigments can be used. Specifically, titanium oxide, zinc sulfide, zinc white, lead white, lithopone, carbon black, oil smoke, navy blue, phthalocyanine blue, ultramarine blue, carmine FB% yellow lead,
Typical examples include zinc yellow, handy yellow, ocher, red iron, and insoluble metal-containing azo dyes. In particular, in the present invention, zinc sulfide, which has a low ultraviolet absorption rate,
Suitable dyes include oil smoke, ultramarine blue, phthalocyanine blue, carmine FB, yellow lead, ocher, red iron, and insoluble metal-containing azo dyes. The amount of color dye and pigment blended in the resulting coating film is 40%.
It is suitably less than % by weight, and the lower limit is arbitrarily determined depending on the desired hiding power and coloring power of the coating film. The extender pigments that may be blended as necessary include silicates,
Examples include talc, kaolin, barium sulfate, and calcium carbonate. The above-mentioned solvents are used to appropriately adjust the viscosity of the inner bag, and include tolutin, xylene, ersetone,
Methyl J thyl ketone, ethyl chlorate, etc. are representative monokichi 1
−． The coating viscosity is preferably 1.5 Voys F or less, preferably L < 1.
5. Next, a method for surface treatment of a porous substrate using the ultraviolet curable paint of the present invention will be explained. It is an organic or organic material with a large number of narrow grooves or conduits, and it is a base material that has the property of being easily absorbed when it comes into contact with liquid materials during boat fishing. Specifically, inorganic substrates such as calcium silicate boards, wood wool cement boards, concrete boards, gypsum boards, and glass fiber boards; wood boards such as plywood and verdicle boards; typical examples include paper and cloth with rough surfaces. Examples include, but are not limited to, these 17. A flow coater roll is applied to the surface of such a porous base material.
Yuichi, spraying, dipping, etc. 9! Nunote 1-! )i;- from the ultraviolet curing Ili'! Paint is applied to the entire surface and impregnated (
-ru. Then, if necessary, set the setting for a lower number of seconds...for several minutes. 'a
Cure the film. Furthermore, the light source used to irradiate ultraviolet light,! ．． . Low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, carbon black, xenon lamps, umical lamps, etc. are used. Manual power can be determined arbitrarily depending on the porous condition of the base material, etc., but it is usually 80w/em or more, preferably 120w/el for <1,2
l1 or more, the metal halide lamp is particularly suitable as the light source. The high-purity base material that has been surface-treated in step 1 can be used as a product as it is, or it can be processed by applying a layer paint or laminating patterned paper or sheets. Products can be marked. =1 Paints include organic solvent-based paints such as acrylic urethane, amino, nonolkyd, and lacquer; water-based paints such as acrylic and vinyl acetate; unsaturated, i! 17
Various paints such as UV-curable paints such as Esdel-based, acrylic urethane-based, and acrylate-based paints can be used. When laminating, use a 1:tooth-1 adhesive such as vinyl acetate, acrylic, synthetic rubber, or epoxy adhesive. <Effects of the Invention> The present invention treats the surface of a porous substrate with an ultraviolet curable coating containing a titanocene compound as a photoreaction initiator, which was thought to be impossible with conventional ultraviolet curable coatings. , it is possible to cure the paint that has penetrated into the porous interior, resulting in poor adhesion and bleeding due to poor coating film curing.
This method prevents the occurrence of pinholes, etc., and is an innovative method for surface treatment of porous substrates. (Examples) Hereinafter, the present invention will be further explained in detail by examples. In the examples, "parts" are expressed on a weight basis. [Preparation of Aku1-Nor Urethane Oligomer (1) J 1 mole of isophorone diisocyanate and 2 moles of 2-hydroxyethyl acrylate were subjected to an addition reaction using a conventional method to prepare Aku1-Nor urethane oligomer (1) with an average molecular weight of 500 17 Ta. [Preparation of acrylic 1-notane oligomer (II)] 1.
2.1 moles of 6-hexanediol, 1 mole of J-ethylene glycol, and 2.4 moles of adipic acid were subjected to a condensation reaction to produce a polyester having a molecular weight of 1000. 1 mol of said polyester 9, 2 mol of isophorone diisocyanate, 2-
A polyester type acrylic urethane oligomer (■) having an average molecular weight of 1,700 was prepared by addition reaction with 2 moles of hydroxyethyl acrylate in a conventional manner. [Preparation of rcryl urethane oligomer (■)] Screw 7t
Nol A-type jepoxy compound (manufactured by Yuka Sil Eboxy Co., Ltd., trade name "Ebi D-") 828J Molecular Bond Approximately 3801 1-Tyl and 2 moles of acrylic acid were subjected to an addition reaction using a conventional method, acrylate 1 having an acid value of 20, Sea oligomer (III) was prepared. [Bis(Sita
1 mole of sodium metal is placed in the 1-Y canol of 'sil4x-2,3,5,6-titrafluorophyl)-titanium, The temperature of the mixture was maintained at approximately 45 υ by cooling the outside. After the reaction had subsided, the solution of 2 ゛ was heated to 50° C. with stirring until completely dissolved. Approximately 42° [1 of
．． The mixture was poured into 11 pentafluorobenzene, heated to 70° C. for 7 hours, and allowed to react. After cooling, it was poured into the same amount of water and extracted with the same amount of methylenetalolide. The organic layer was separated, dried with sulfuric acid, and methylenetalolide was distilled under reduced pressure to obtain l'#al,
Decyl (2□ 3.5.6-thitrafluoroicol 84-
Made by chloro) phenyl ether. The obtained decyl(2,3,5,6-・tetrafluoro-
2 moles of 4-chloro)phenyl ether were dissolved in anhydrous diethyl ether under an inert gas atmosphere. This solution was cooled to 75°C in MIL, and then a hexane solution of lithium butyl was added dropwise at the same temperature.
Stir for 5 minutes1. Ta. Next, 1 mol of bis(cyclopentagenyl)titanium dichloride is added in the form of a powder. The mixture was warmed to room temperature over 2 hours to allow the reaction to proceed. The reaction product was poured into twice the amount of water and extracted several times with 1-1 ethyl acetate. The ethyl acetate phase was dried over IJum and distilled under reduced pressure, and the resulting residue was purified by chromatography on silica gel using a hexane-ethyl mixture as the mobile phase, and the solvent was then evaporated. Bis(cyclopentagenyl)-bis(4-decyloxy-2,3,5,6-detrafluorof-5.yl)-titanium was converted to 41. Ta. [Bis(cyclopentagenyl)-bis(pentaful)
, 40 Fales) - Titanium Nog 1.
The reaction was carried out in the same manner except that 2 moles of chloropentafluorobenzene was used instead of 2,3,5,6-tetrafluoro4-chloro)phenyl ether. 5-nyl)-titaniuno was prepared. 7 Example 1 Ryogrill urethane oligomer (1) 50fff
12-Ethylhexyl acrylate 50 parts Butyl acetate 20 parts Power → Specific gravity 0
．． 80g/rn'' of ultraviolet curing agent made of the above formulation was applied to the calcium silicate plate of No. 8 by air spray.
After flashing off at 60 t' for 1 minute, the coating was cured by UV irradiation by passing through a metal halide lamp at a passing speed of 15 m/min from a distance of 100,111 m below (manpower: 120 w/am). The surface of the base material was in a state without tack, and then it was lightly polished and fluffed in step 1. After that, 100g of solvent-based acrylic urethane white enamel was applied using S earth spray.
m' application I2.80t, dried for 21) minutes. The finished coated board is flat, and the base material 1 knee r reaches 4
When 25 pieces of m width goblin were cut and subjected to a peeling test of 25/25 and 5+, the adhesion was good. Example 2 Acrylic urethane oligomer (II), 10 parts phenoxy acrylic) 30! 'f
f1N-vinylpyrrolidone 30 parts 60
g/m' of wood-grain printed tissue paper was coated with an ultraviolet curable paint consisting of the following formulation at 40 g/rr using a roll coater.
+'' coating and after setting for 1 minute, pass through a metal halide lamp (input 120w/cm) (passing speed 7.5 m/mi from a position 100 m below D) and cure the @ film by UV irradiation. The surface of the base material was free of tack, and the wood grain paper was glossy.Next, a vinyl acetate adhesive was applied, and the dried plywood was hot-pressed with the wood grain paper. The obtained decorative board was cut into 10 pieces with a width of <1 mm to reach the base material.
0 pieces cut! 7. When the seven Rohan deep strips were peeled off, the result was 100/IDO, indicating good adhesion. Example: 1 Same as Example 2 except that acrylic]boxy oligomer (III) was blended as the ultraviolet a-curable coating component instead of T-Krylu 1/tan oligomer (II). -I made a decorative board. The obtained decorative board had an excellent appearance similar to that of Example 2.
．． was. Also, the adhesion test was 9? /1 O0 was somewhat inferior, but had adhesion that did not pose a problem in practical use. Example 4 In Example 2, ultraviolet curing type
- A decorative board was made in the same manner, except that it was applied by spraying at a rate of 80 g/m'. The resulting decorative board has a glossy apricot texture of -1-1L.
Specularity, l-, peeling, adhesion test also 100/l
OOT: "4・Passing・) Adhesion was good. Comparative Example 1 In Example 2, the UV-curable medium 4-component composition 1..C
α in place of the photoinitiator bis(cyclopentashnyl)-bis(4-decyloxy-2,3,5,6-titrafluorophenyl)-titanium. A decorative board was prepared in the same manner except that an ultraviolet curable paint containing only 3 parts of α-dimethyl-α-hydrohydro-T ± tofuunone was used. The obtained decorative board had the same appearance as in Example 2.
, was. However, the adhesion test was O/100, indicating poor adhesion. Example 5 γ Acrylic urethane oligomer (II) 40 parts Calcium carbonate 508B Butyl acetate 30 parts An ultraviolet curable paint consisting of the formulation shown in F was applied to a medium specific gravity fiberboard with a specific gravity of 0.6.
- Spray 80g/door arm cloth 1, 5.60℃, flash off for 1 minute, then metal halide lamp (input 12)
The coating film was cured by UV irradiation by passing it once at a passing speed of 15 rn/a+in from a position of 10 tss below 1 (0 w/cm).Then, the surface was polished with a #320 inch sandbever.
? After smoothing, the solvent-based acrylic urethane white enamel was dried using air spray at 100 g/11] at 111.80° C. for 20 minutes. The painted plate is smooth and reaches the base material <2+v
Cut 450 pieces of srh goban 1. Cellophane tape peel test 1.1. It was 5015 O, and the adhesion was good. Comparative Example 2 In Example 5, ultraviolet curable paint components and 1. Proceed in the same manner except that 3 parts and 10 parts of benzophenone were added in place of the photoreaction initiator bis(cyclopentadienyl)bis(pentafluorophenyl)-99nium, and an ultraviolet curable paint was used. I got a painted plate. The obtained painted plate was smooth and smooth as in Example 5! , ゛ is,
When an adhesion test was conducted, the surface layer of the fiberboard was destroyed and the adhesion was poor.

Claims (2)

[Claims] (1) Applying an ultraviolet curable paint containing a titanocene compound as a photoreaction initiator to a porous substrate, irradiating it with ultraviolet light,
A method for surface treatment of porous substrates to cure the coating film. (2) The method for surface treatment of a porous substrate according to claim (1), wherein the vehicle component of the ultraviolet curable paint contains an acrylic urethane oligomer as a main component.