WO2018034116A1 - Water-absorbing sheet - Google Patents
Water-absorbing sheet Download PDFInfo
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- WO2018034116A1 WO2018034116A1 PCT/JP2017/026984 JP2017026984W WO2018034116A1 WO 2018034116 A1 WO2018034116 A1 WO 2018034116A1 JP 2017026984 W JP2017026984 W JP 2017026984W WO 2018034116 A1 WO2018034116 A1 WO 2018034116A1
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- Prior art keywords
- water
- acrylic monomer
- film
- absorbent sheet
- mass
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
Definitions
- the present invention relates to a water-absorbent sheet having high transparency.
- Patent Document 1 As water-absorbent sheets such as disposable diapers and pet sheets that require high water absorption, acrylate polymer particles are dispersed on a substrate and fixed with a covering binder (Patent Document 1).
- the water absorbent sheet As a new use of the water absorbent sheet, it is considered to be applied to a window glass or a transparent display. In that case, the haze degree exceeds 8% as a practical transparency for the water absorbent sheet. It is required that the manufacturing cost does not increase excessively because it is applied to a relatively large area.
- the conventional water-absorbent sheet has a relatively large acrylate polymer particle that is relatively low in cost than the wavelength of visible light, even if a transparent material is used as a base material or a coating binder. Since it has a diameter, it may appear cloudy or the outer shape of the polymer may be visible, and the desired transparency cannot be obtained.
- An object of the present invention is to solve the above-described problems of the prior art, and to provide a water-absorbent sheet that has high transparency before and after water absorption and can be manufactured at low cost.
- the present inventor has photocured a water-containing acrylic monomer film formed from a water-containing composition in which water is mixed with a water-soluble acrylic monomer component that shows transparency under a predetermined water-containing condition while maintaining the water-containing state. It was found that the water-absorbent sheet thus obtained can realize unexpectedly good transparency and water-absorbency at the same time, and completed the present invention.
- the present invention is a water absorbent sheet having a water-containing photocured film of a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water,
- a water-absorbent sheet characterized in that a water-soluble acrylic monomer component exhibits transparency when mixed with 18% by mass or more of water at 23 ° C.
- the present invention also provides a method for producing a water-absorbent sheet having a water-containing photocured film of a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water:
- a water-containing photocurable acrylic monomer composition comprising a water-soluble acrylic monomer component that exhibits transparency when mixed with 18% by mass or more of water at 23 ° C., a photopolymerization initiator, a crosslinking agent, and water.
- the water-absorbent sheet of the present invention has a water-containing photocured film of a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water, and 18 mass at 23 ° C. as the water-soluble acrylic monomer component. Use one that shows transparency when mixed with more than% water.
- a water-soluble acrylic monomer component is composed of a water-soluble acrylic monomer that exhibits transparency when mixed with at least 18% by mass of water at 23 ° C. and is relatively easy to obtain at low cost. . For this reason, the water-absorbent sheet of the present invention can simultaneously achieve good water absorption and transparency.
- the water absorbent sheet of the present invention has a water-containing photocured film of a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water.
- the water absorbent sheet of the present invention may have a single layer structure of this water-containing photocured film.
- stacked on the base film which may be transparent may be sufficient.
- stacked on the surface of the water-containing photocured film on the opposite side to a base film may be sufficient as the peeling film which is transparent and functions also as a protective sheet.
- the term “acrylic” includes “methacrylic”.
- the water-soluble acrylic monomer component exhibits transparency when mixed with 18% by mass or more of water at 23 ° C. For this reason, when the water-containing acrylic monomer film is photocured to form a water-containing photocured film, good transparency can be realized.
- the evaluation temperature was set to “23 ° C.” because the atmospheric temperature in a general production process was 23 ° C., and the mixing amount of water was set to “18% by mass or more” This is because, even after the monomer film is irradiated with ultraviolet rays, the photocuring component (polymers) is used as an index that can maintain transparency without being eluted from water.
- water-soluble in the water-soluble acrylic monomer component means that the monomer component is miscible with water at any ratio without layer separation or the like.
- the measurement can be performed by a “mixing experiment” of confirming the water-soluble acrylic monomer component with respect to water while gradually increasing the amount of addition.
- “showing transparency” of the water-soluble acrylic monomer component means that the haze degree (haze) measured according to JIS K7136 is 8% or less, preferably 5% or less.
- the water-soluble acrylic monomer component contains one or more water-soluble acrylic monomers, and when it contains a plurality of water-soluble acrylic monomers, all these water-soluble acrylic monomer components are at 23 ° C. As described above, it is preferable that it exhibits transparency when mixed with 18% by mass or more of water in that transparency is maintained even after irradiation with ultraviolet rays.
- Water-soluble acrylic monomer As such a water-soluble acrylic monomer, a known water-soluble acrylic monomer having a hydrophilic group such as a carboxy group, an amino group, a hydroxyl group, or a polyether group is used.
- water-soluble acrylic monomers include hydroxyl-containing acrylic monomers such as 4-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxyethyl methacrylate from the viewpoint of transparency of the water-containing photocured film. be able to. These may be used as a mixture or may be used alone.
- the water-soluble acrylic monomer component may be various hydrophilic monomers in addition to the above-mentioned hydroxyl group-containing acrylic monomer as long as it shows transparency when mixed with 18% by mass or more of water at 23 ° C.
- the various hydrophilic monomers include vinyl alcohol, vinyl acetate, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid amide, and the like.
- a hydrophilic group such as a hydroxy group, a carboxyl group, or a polyether group may be bonded to these hydrophilic monomers as necessary. Of these, hydroxyethylacrylamide and acrylic acid can be preferably mentioned.
- the sheet hardness of the water-absorbent sheet can be adjusted, and tackiness can be weakened. As a result, it becomes possible to manufacture a water-absorbent sheet by roll-to-roll.
- a (meth) acrylamide quaternary ammonium salt monomer represented by the following formula (1) can be used as the hydrophilic monomer.
- this monomer high water absorption can be imparted to the water-absorbing polymer sheet of the present invention, and tackiness in the water-absorbing sheet in which the water-containing state is maintained can be suppressed or adjusted.
- R 1 and R 2 are each independently a hydrogen atom or a lower alkyl group.
- R 3 and R 4 are a lower alkyl group,
- R 5 is a lower alkyl group, a lower alkenyl group or a benzyl group,
- A is a lower alkylene group, and
- X ⁇ is a halogen anion or a perchlorate anion.
- examples of the lower alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a Sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Of these, a methyl group is preferred.
- examples of the lower alkenyl group include ethenyl group, 1 or 2-propenyl group, 1,2 or 3-butenyl group, 1,2,3 or 4-pentenyl group, 1,2,3,4, 5-hexenyl group and the like. Can be mentioned.
- Examples of the lower alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.
- Examples of the halogen anion include chloro anion, bromo anion, and iodo anion.
- Preferred R 1 is a hydrogen atom
- preferred R 2 is a methyl group
- preferred R 3 , R 4 and R 5 are methyl groups
- preferred A is a propylene group
- preferred X ⁇ is a chloroanion.
- specific examples of the cation moiety of the (meth) acrylamide-based quaternary ammonium salt monomer include acryloylaminomethyltrimethylammonium, acryloylaminomethyltriethylammonium, acryloylaminomethyltripropylammonium, acryloylaminoethyltrimethylammonium, acryloylaminopropyl.
- Trimethylammonium Trimethylammonium, acryloylaminopropylmethyldiethylammonium, acryloylaminopropylethyldimethylammonium, acryloylaminopropylmethyldipropylammonium, acryloylaminopropyltriethylammonium, acryloylaminopropyltripropylammonium, acryloylaminoethyldimethylbenzylammonium, acryloyl Mino dimethyl benzyl ammonium, acrylamide-based quaternary ammonium cations, such as acryloyl aminopropyl diethyl benzyl ammonium.
- acryloylaminopropyltrimethylammonium and acryloylaminopropyldimethylbenzylammonium are preferred because inexpensive industrial raw materials are easily available. Particularly preferred is acryloylaminopropyltrimethylammonium.
- preferable (meth) acrylamide type quaternary ammonium salt monomer of the formula (1) includes acryloylaminopropyltrimethylammonium chloride, in other words, dimethylaminopropylacrylamide methyl chloride salt.
- Water-containing acrylic monomer film Such a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water is obtained by calendering a water-containing photocurable acrylic monomer composition containing at least a water-soluble acrylic monomer component and water as described later.
- the film is formed by a conventional method such as a method.
- the film thickness varies depending on the use of the water-absorbent sheet, but is usually 10 to 1000 ⁇ m, preferably 50 to 500 ⁇ m.
- the water content in such a water-containing acrylic monomer film is substantially the same as the water content of a water-containing photocured film described later, from the viewpoint of mechanical strength required as a water-absorbent sheet and handling in the manufacturing process. Adjusted.
- the water content is preferably in the range of 5 to 50% by mass. Within this range, coupled with the fact that the water-soluble acrylic monomer component is miscible with 18% by mass or more of water, there is an effect that the haze degree of the water-containing photocured film after being irradiated with ultraviolet rays can be reliably reduced. can get.
- water distilled water and ion-exchange water can be used preferably.
- the water content can be measured by measuring a change in weight by heating weighing.
- the water-containing acrylic monomer film usually contains a photopolymerization initiator. This is to accelerate the curing of the monomer film.
- membrane contains a crosslinking agent further. This is to increase the water holding power of the water-containing photocured film and to impart mechanical strength to the water-containing photocured film that enables the water-containing photocured film to be wound up by roll-to-roll.
- a known radical photopolymerization initiator can be employed.
- benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and anisole methyl ether, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone (Darocur 2959; BASF Japan Ltd.), ⁇ -hydroxy- ⁇ , ⁇ ′-dimethylacetophenone (Darocur 1173; BASF Japan Ltd.), methoxyacetophenone, 2,2′-dimethoxy-2-phenylacetophenone (Irgacure) 651; BASF Japan K.K.), 2-hydroxy-2-cyclohexylacetophenone (Irgacure 184; BASF Japan K.K.), 2,2-diethoxyacetophenone, 2,2-di- Acetophenones such as toxi
- crosslinking agent a known crosslinking agent can be employed, and a polyfunctional acrylate-based crosslinking agent can be preferably used.
- a polyfunctional acrylate-based crosslinking agent can be preferably used.
- the blending amount of the photopolymerization initiator in the water-containing acrylic monomer film is preferably 0.01 to 1 part by mass, more preferably 0.1 to 0.5 part by mass with respect to 100 parts by mass of the water-soluble acrylic monomer component described above. Part. If it is this range, favorable film formability is realizable. Further, the blending amount of the crosslinking agent in the water-containing acrylic monomer film is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the water-soluble acrylic monomer component described above. is there. Within this range, good water absorption and dissolution resistance can be realized.
- the water absorbent sheet of the present invention contains a water-containing photocured film derived from the water-containing acrylic monomer film described above.
- the photo-curing of the water-containing acrylic monomer film can be performed by irradiating the water-containing acrylic monomer film with ultraviolet rays as will be described later.
- the film thickness varies depending on the use of the water-absorbent sheet, but is usually 10 to 1000 ⁇ m, preferably 50 to 500 ⁇ m.
- the water content of the water-containing photocured film depends on the water content of the water-containing acrylic monomer film, but is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. If it is this range, favorable film formability is realizable.
- the water content of the water-containing photocured film can be measured by the same method as the measurement of the water content of the water-containing acrylic monomer film.
- the haze degree of the hydrous photocured film according to JIS K7136 is preferably 8% or less, more preferably 5% or less. If it is this range, favorable transparency is realizable.
- the water absorption of the water-containing photocured film is preferably 10% by mass or more, more preferably 50% by mass or more based on its own weight. If it is this range, dew condensation prevention etc. are realizable.
- the water-containing photocured film of the water-absorbent sheet of the present invention is a transparent thermoplastic resin compatible with the water-containing photocured film, an antioxidant, a light stabilizer, a polymerization inhibitor, as long as the effects of the present invention are not impaired.
- Silane coupling agents, dyes and the like can be contained.
- the water absorbent sheet of the present invention having a water-containing photocured film of a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water should be produced by a production method having the following steps (A) to (C). Can do.
- a water-containing acrylic monomer film is formed by forming a water-containing photocurable acrylic monomer composition on a base film.
- the water-containing acrylic monomer film can be formed using a known method. For example, it can be performed by applying a water-containing photocurable acrylic monomer composition to a base film such as a polyethylene terephthalate film subjected to a release treatment by a known method such as a calendar method or a bar coater method.
- the base film is transparent (ultraviolet ray transmissive) so that the ultraviolet ray can be irradiated in the step C described later.
- the water-containing photocurable acrylic monomer composition contains a water-soluble acrylic monomer component, a photopolymerization initiator, a crosslinking agent, and water.
- the types and blending ratios of these components are as described in relation to the water absorbent sheet of the present invention.
- the water-soluble acrylic monomer component one that exhibits transparency when mixed with 18% by mass or more of water at 23 ° C., specifically, one having a haze degree of 8% or less according to JIS K7136 is used. To do. This is for realizing good transparency when the water-containing acrylic monomer film is photocured to form a water-containing photocured film.
- the water-containing photocurable acrylic monomer composition is a transparent thermoplastic resin that is compatible with the water-containing photocured film after photocuring, an antioxidant, a light stabilizer, a polymerization inhibitor, and a silane coupling agent. , Dyes and the like can be contained.
- a transparent release film is laminated on the water-containing acrylic monomer film. By laminating this film, it can be photocured while maintaining the water content of the water-containing acrylic monomer film in the following step C.
- a known transparent release film can be used.
- a commercially available release-treated polyethylene terephthalate film or the like can be used.
- the “transparent” of the transparent release film means that the ultraviolet rays used in Step C described later are transmitted.
- a water-containing photocured film is formed while maintaining the water content of the water-containing acrylic monomer film.
- Ultraviolet irradiation can be performed by applying a known ultraviolet irradiation technique. For example, it can be carried out by irradiating the water-containing acrylic monomer film with ultraviolet rays emitted from a chemical lamp, a high-pressure mercury lamp or the like from the transparent release film or base film side.
- the chemical lamp adjusted to 0.5 to 1.5 mW / cm 2 is irradiated with the ultraviolet ray for 5 to 10 minutes, and then, the light intensity of 1000 to 1500 mJ / cm 2 with the high pressure mercury lamp. And irradiation.
- the water content of the hydrated acrylic monomer film is “maintained” means that the moisture content contained in the hydrated acrylic monomer film before the ultraviolet irradiation and the moisture content contained in the hydrated photocured film after the ultraviolet irradiation. Means substantially the same amount. Further, whether or not the water content of the water-containing acrylic monomer film is maintained can be evaluated by a method similar to a known method for measuring the water content of the water-containing acrylic monomer film.
- the water-absorbent sheet having a water-containing photocured film thus prepared can be preferably used by removing the transparent release film and attaching it to an adherend such as a transparent display.
- Comparative Example 1 88 parts by mass of acrylic monomers shown in Table 2, 12 parts by mass of water, 0.3 parts by mass of a photopolymerization initiator (Darocur 1173, BASF Japan Ltd.), and a crosslinking agent (M-400, Toagosei Co., Ltd.) ) 0.3 parts by mass was uniformly mixed using a rotary blade stirrer (Three-One Motor, Shinto Kagaku Co., Ltd.) to prepare a water-containing photocurable acrylic monomer composition.
- a photopolymerization initiator Darocur 1173, BASF Japan Ltd.
- M-400 Toagosei Co., Ltd.
- This water-containing photocurable acrylic monomer composition was applied to a release-treated polyethylene terephthalate film with a thickness of 200 ⁇ m using a bar coater, and another release-treated polyethylene terephthalate film was placed thereon.
- UV light main wavelength: 365 nm
- a chemical lamp adjusted to 1 mW / cm 2 with respect to a film of a water-containing photocurable acrylic monomer composition sandwiched between two release-treated polyethylene terephthalate films (that is, a water-containing acrylic monomer film)
- a water absorbent sheet was prepared. Note that the water content of the water-containing photocurable acrylic monomer composition film in the water-absorbent sheets of Examples 1 to 3 and Comparative Example 1 and the water content of the cured water-containing photocured film were both approximately 12% ( Mass basis) and there was no substantial difference.
- the water-absorbent sheets of Examples 1 to 3 were excellent in transparency and exhibited good water absorption.
- the water absorption rate of the water absorbent sheet can be controlled by changing the type of the water-soluble acrylic monomer.
- the water-absorbent sheet of Comparative Example 1 uses 2-hydroxybutyl acrylate as a water-soluble acrylic monomer, as shown in Table 1, which becomes cloudy when mixed with 18 parts by mass of water at 23 ° C. Therefore, a problem occurred in the transparency of the water absorbent sheet.
- the water-absorbent sheet of the present invention exhibits good water absorption, and also exhibits good transparency, specifically a haze degree of 8% or less. Therefore, it is useful as a water-absorbing material applied to window glass, transparent displays and the like.
Abstract
A water-absorbing sheet has a water-containing photocuring film of a water-containing acrylic monomer film that contains a water-soluble acrylic monomer component and water. The water-soluble acrylic monomer component exhibits transparency when mixed with 18 mass% or more of water at 23°C. More specifically, transparency with a haze of 8% or less. It is preferable that all of the water-soluble acrylic monomers that constitute part of the water-soluble acrylic monomer component exhibit transparency even when mixed with 18 mass% or more of water at 23°C. Examples of such water-soluble acrylic monomers include hydroxy-group-containing acrylic monomers, and in particular, 4-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, or 2-hydroxyethyl methacrylate.
Description
本発明は、高い透明性を有する吸水性シートに関する。
The present invention relates to a water-absorbent sheet having high transparency.
高い吸水性が要求される紙おむつやペットシーツ等の吸水性シートとして、アクリル酸塩系ポリマー粒子を基材上に散布し、被覆結合材で固定したものが提案されている（特許文献１）。
As water-absorbent sheets such as disposable diapers and pet sheets that require high water absorption, acrylate polymer particles are dispersed on a substrate and fixed with a covering binder (Patent Document 1).
ところで、吸水性シートの新たな用途として、窓ガラスや透明ディスプレイに適用することが考えられているが、その場合、吸水性シートに対しては、実用的な透明度としてヘイズ度が８％を超えないことや、比較的大きな面積への適用であるため製造コストが過度に増加しないことが求められている。しかしながら、従来の吸水性シートは、基材や被覆結合材として透明材料を使用したとしても、比較的低コストで入手可能なアクリル酸塩系ポリマー粒子が可視光線の波長よりも相対的に大きな粒径を有するため、白濁して見えたり、ポリマーの外形が見えたりし、所期の透明性が得られないという問題があった。
By the way, as a new use of the water absorbent sheet, it is considered to be applied to a window glass or a transparent display. In that case, the haze degree exceeds 8% as a practical transparency for the water absorbent sheet. It is required that the manufacturing cost does not increase excessively because it is applied to a relatively large area. However, the conventional water-absorbent sheet has a relatively large acrylate polymer particle that is relatively low in cost than the wavelength of visible light, even if a transparent material is used as a base material or a coating binder. Since it has a diameter, it may appear cloudy or the outer shape of the polymer may be visible, and the desired transparency cannot be obtained.
本発明の目的は、以上の従来の技術の問題点を解決することであり、吸水前後で高い透明性を有し、低コストで製造可能な吸水性シートを提供することである。
An object of the present invention is to solve the above-described problems of the prior art, and to provide a water-absorbent sheet that has high transparency before and after water absorption and can be manufactured at low cost.
本発明者は、所定の含水条件下で透明性を示す水溶性アクリル系モノマー成分に水を配合した含水組成物から成膜した含水アクリル系モノマー膜を、その含水状態を保ったまま光硬化させることにより得られる吸水性シートが、予想外にも良好な透明性と吸水性とを同時に実現できることを見出し、本発明を完成させるに至った。
The present inventor has photocured a water-containing acrylic monomer film formed from a water-containing composition in which water is mixed with a water-soluble acrylic monomer component that shows transparency under a predetermined water-containing condition while maintaining the water-containing state. It was found that the water-absorbent sheet thus obtained can realize unexpectedly good transparency and water-absorbency at the same time, and completed the present invention.
即ち、本発明は、水溶性アクリル系モノマー成分と水とを含有する含水アクリル系モノマー膜の含水光硬化膜を有する吸水性シートであって、
水溶性アクリル系モノマー成分が、２３℃で１８質量％以上の水と混和したときに透明性を示すものであることを特徴とする吸水性シートを提供する。 That is, the present invention is a water absorbent sheet having a water-containing photocured film of a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water,
Provided is a water-absorbent sheet characterized in that a water-soluble acrylic monomer component exhibits transparency when mixed with 18% by mass or more of water at 23 ° C.
水溶性アクリル系モノマー成分が、２３℃で１８質量％以上の水と混和したときに透明性を示すものであることを特徴とする吸水性シートを提供する。 That is, the present invention is a water absorbent sheet having a water-containing photocured film of a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water,
Provided is a water-absorbent sheet characterized in that a water-soluble acrylic monomer component exhibits transparency when mixed with 18% by mass or more of water at 23 ° C.
また、本発明は、水溶性アクリル系モノマー成分と水とを含有する含水アクリル系モノマー膜の含水光硬化膜を有する吸水性シートの製造方法であって：
２３℃で１８質量％以上の水と混和したときに透明性を示す水溶性アクリル系モノマー成分と、光重合開始剤と、架橋剤と、水とを含有する含水光硬化性アクリル系モノマー組成物をベースフィルムに成膜することにより含水アクリル系モノマー膜を形成する工程；
含水アクリル系モノマー膜に透明剥離フィルムを積層する工程；及び
含水アクリル系モノマー膜に対し、透明剥離フィルム若しくはベースフィルム側から紫外線を照射することにより、含水アクリル系モノマー膜の含水量を保持したまま含水光硬化膜を形成する工程；
を有する製造方法を提供する。 The present invention also provides a method for producing a water-absorbent sheet having a water-containing photocured film of a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water:
A water-containing photocurable acrylic monomer composition comprising a water-soluble acrylic monomer component that exhibits transparency when mixed with 18% by mass or more of water at 23 ° C., a photopolymerization initiator, a crosslinking agent, and water. Forming a water-containing acrylic monomer film by forming a film on the base film;
A step of laminating a transparent release film on the water-containing acrylic monomer film; and irradiating the water-containing acrylic monomer film with ultraviolet rays from the transparent release film or the base film side, while maintaining the water content of the water-containing acrylic monomer film Forming a hydrous photocured film;
A production method is provided.
２３℃で１８質量％以上の水と混和したときに透明性を示す水溶性アクリル系モノマー成分と、光重合開始剤と、架橋剤と、水とを含有する含水光硬化性アクリル系モノマー組成物をベースフィルムに成膜することにより含水アクリル系モノマー膜を形成する工程；
含水アクリル系モノマー膜に透明剥離フィルムを積層する工程；及び
含水アクリル系モノマー膜に対し、透明剥離フィルム若しくはベースフィルム側から紫外線を照射することにより、含水アクリル系モノマー膜の含水量を保持したまま含水光硬化膜を形成する工程；
を有する製造方法を提供する。 The present invention also provides a method for producing a water-absorbent sheet having a water-containing photocured film of a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water:
A water-containing photocurable acrylic monomer composition comprising a water-soluble acrylic monomer component that exhibits transparency when mixed with 18% by mass or more of water at 23 ° C., a photopolymerization initiator, a crosslinking agent, and water. Forming a water-containing acrylic monomer film by forming a film on the base film;
A step of laminating a transparent release film on the water-containing acrylic monomer film; and irradiating the water-containing acrylic monomer film with ultraviolet rays from the transparent release film or the base film side, while maintaining the water content of the water-containing acrylic monomer film Forming a hydrous photocured film;
A production method is provided.
本発明の吸水性シートは、水溶性アクリル系モノマー成分と水とを含有する含水アクリル系モノマー膜の含水光硬化膜を有しており、その水溶性アクリル系モノマー成分として、２３℃で１８質量％以上の水と混和したときに透明性を示すものを使用する。このような水溶性アクリル系モノマー成分は、少なくとも、２３℃で１８質量％以上の水と混和したときに透明性を示し、比較的容易で低コストで入手可能な水溶性アクリル系モノマーから構成する。このため、本発明の吸水性シートは、良好な吸水性と透明性とを同時に実現することができる。
The water-absorbent sheet of the present invention has a water-containing photocured film of a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water, and 18 mass at 23 ° C. as the water-soluble acrylic monomer component. Use one that shows transparency when mixed with more than% water. Such a water-soluble acrylic monomer component is composed of a water-soluble acrylic monomer that exhibits transparency when mixed with at least 18% by mass of water at 23 ° C. and is relatively easy to obtain at low cost. . For this reason, the water-absorbent sheet of the present invention can simultaneously achieve good water absorption and transparency.
以下、本発明の吸水性シートを詳細に説明する。
Hereinafter, the water absorbent sheet of the present invention will be described in detail.
＜吸水性シート＞
本発明の吸水性シートは、水溶性アクリル系モノマー成分と水とを含有する含水アクリル系モノマー膜の含水光硬化膜を有する。本発明の吸水性シートは、この含水光硬化膜の単層構造であってもよい。また、透明であってもよいベースフィルムに含水光硬化膜が積層されている構造であってもよい。更に透明で保護シートとしても機能する剥離フィルムが、ベースフィルムと反対側の含水光硬化膜の表面に積層されている構造であってもよい。なお、本発明において「アクリル系」という用語は、「メタクリル系」を包含する。 <Water absorbent sheet>
The water absorbent sheet of the present invention has a water-containing photocured film of a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water. The water absorbent sheet of the present invention may have a single layer structure of this water-containing photocured film. Moreover, the structure where the water-containing photocured film | membrane is laminated | stacked on the base film which may be transparent may be sufficient. Furthermore, the structure which is laminated | stacked on the surface of the water-containing photocured film on the opposite side to a base film may be sufficient as the peeling film which is transparent and functions also as a protective sheet. In the present invention, the term “acrylic” includes “methacrylic”.
本発明の吸水性シートは、水溶性アクリル系モノマー成分と水とを含有する含水アクリル系モノマー膜の含水光硬化膜を有する。本発明の吸水性シートは、この含水光硬化膜の単層構造であってもよい。また、透明であってもよいベースフィルムに含水光硬化膜が積層されている構造であってもよい。更に透明で保護シートとしても機能する剥離フィルムが、ベースフィルムと反対側の含水光硬化膜の表面に積層されている構造であってもよい。なお、本発明において「アクリル系」という用語は、「メタクリル系」を包含する。 <Water absorbent sheet>
The water absorbent sheet of the present invention has a water-containing photocured film of a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water. The water absorbent sheet of the present invention may have a single layer structure of this water-containing photocured film. Moreover, the structure where the water-containing photocured film | membrane is laminated | stacked on the base film which may be transparent may be sufficient. Furthermore, the structure which is laminated | stacked on the surface of the water-containing photocured film on the opposite side to a base film may be sufficient as the peeling film which is transparent and functions also as a protective sheet. In the present invention, the term “acrylic” includes “methacrylic”.
（水溶性アクリル系モノマー成分）
本発明において、水溶性アクリル系モノマー成分は、２３℃で１８質量％以上の水と混和したときに透明性を示すものである。このため、含水アクリル系モノマー膜を光硬化させて含水光硬化膜とした際に良好な透明性を実現することができる。なお、評価温度を「２３℃」としたのは、一般的な製造工程における雰囲気温度が２３℃だからであり、また、水の混和量を「１８質量％以上」としたのは、含水アクリル系モノマー膜に紫外線を照射した後においても、光硬化成分（ポリマー類）が水から溶出することなく透明性を維持できる程度の指標とするためである。 (Water-soluble acrylic monomer component)
In the present invention, the water-soluble acrylic monomer component exhibits transparency when mixed with 18% by mass or more of water at 23 ° C. For this reason, when the water-containing acrylic monomer film is photocured to form a water-containing photocured film, good transparency can be realized. The evaluation temperature was set to “23 ° C.” because the atmospheric temperature in a general production process was 23 ° C., and the mixing amount of water was set to “18% by mass or more” This is because, even after the monomer film is irradiated with ultraviolet rays, the photocuring component (polymers) is used as an index that can maintain transparency without being eluted from water.
本発明において、水溶性アクリル系モノマー成分は、２３℃で１８質量％以上の水と混和したときに透明性を示すものである。このため、含水アクリル系モノマー膜を光硬化させて含水光硬化膜とした際に良好な透明性を実現することができる。なお、評価温度を「２３℃」としたのは、一般的な製造工程における雰囲気温度が２３℃だからであり、また、水の混和量を「１８質量％以上」としたのは、含水アクリル系モノマー膜に紫外線を照射した後においても、光硬化成分（ポリマー類）が水から溶出することなく透明性を維持できる程度の指標とするためである。 (Water-soluble acrylic monomer component)
In the present invention, the water-soluble acrylic monomer component exhibits transparency when mixed with 18% by mass or more of water at 23 ° C. For this reason, when the water-containing acrylic monomer film is photocured to form a water-containing photocured film, good transparency can be realized. The evaluation temperature was set to “23 ° C.” because the atmospheric temperature in a general production process was 23 ° C., and the mixing amount of water was set to “18% by mass or more” This is because, even after the monomer film is irradiated with ultraviolet rays, the photocuring component (polymers) is used as an index that can maintain transparency without being eluted from water.
本発明において、水溶性アクリル系モノマー成分の「水溶性」とは、モノマー成分が層分離等することなく任意の割合で水と混和することを意味する。その測定は、水に対して水溶性アクリル系モノマー成分を徐々にその添加量を増加させながら確認するという「混和実験」により行うことができる。また、水溶性アクリル系モノマー成分の「透明性を示す」とは、ＪＩＳ Ｋ７１３６に準じて測定されるヘイズ度（曇度）で８％以下、好ましくは５％以下を示すことである。
In the present invention, “water-soluble” in the water-soluble acrylic monomer component means that the monomer component is miscible with water at any ratio without layer separation or the like. The measurement can be performed by a “mixing experiment” of confirming the water-soluble acrylic monomer component with respect to water while gradually increasing the amount of addition. Further, “showing transparency” of the water-soluble acrylic monomer component means that the haze degree (haze) measured according to JIS K7136 is 8% or less, preferably 5% or less.
水溶性アクリル系モノマー成分は、一種以上の水溶性アクリル系モノマーを含有しており、複数の水溶性アクリル系モノマーを含有している場合、それらすべての水溶性アクリル系モノマー成分が、２３℃で１８質量％以上の水と混和したときに透明性を示すものであることが、前述したとおり、紫外線を照射した後においても透明性を維持するという点で好ましい。
The water-soluble acrylic monomer component contains one or more water-soluble acrylic monomers, and when it contains a plurality of water-soluble acrylic monomers, all these water-soluble acrylic monomer components are at 23 ° C. As described above, it is preferable that it exhibits transparency when mixed with 18% by mass or more of water in that transparency is maintained even after irradiation with ultraviolet rays.
（水溶性アクリル系モノマー）
このような水溶性アクリル系モノマーとしては、親水性基であるカルボキシ基、アミノ基、水酸基、ポリエーテル基等を有する公知の水溶性アクリル系モノマーを使用する。 (Water-soluble acrylic monomer)
As such a water-soluble acrylic monomer, a known water-soluble acrylic monomer having a hydrophilic group such as a carboxy group, an amino group, a hydroxyl group, or a polyether group is used.
このような水溶性アクリル系モノマーとしては、親水性基であるカルボキシ基、アミノ基、水酸基、ポリエーテル基等を有する公知の水溶性アクリル系モノマーを使用する。 (Water-soluble acrylic monomer)
As such a water-soluble acrylic monomer, a known water-soluble acrylic monomer having a hydrophilic group such as a carboxy group, an amino group, a hydroxyl group, or a polyether group is used.
このような水溶性アクリル系モノマーの具体例としては、含水光硬化膜の透明性の点から４－ヒドロキシブチルアクリレート、２－ヒドロキシプロピルアクリレート、２－ヒドロキシエチルメタクリレート等の水酸基含有アクリル系モノマーを挙げることができる。これらは混合して使用してもよく、単独で使用してもよい。
Specific examples of such water-soluble acrylic monomers include hydroxyl-containing acrylic monomers such as 4-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxyethyl methacrylate from the viewpoint of transparency of the water-containing photocured film. be able to. These may be used as a mixture or may be used alone.
なお、水溶性アクリル系モノマー成分は、２３℃で１８質量％以上の水と混和したときに透明性を示すものである限り、上述の水酸基含有アクリル系モノマーの他に、種々の親水性モノマーであってもよい。種々の親水性モノマーの具体例としては、ビニルアルコール、酢酸ビニル、（メタ）アクリル酸、（メタ）アクリル酸エステル、（メタ）アクリル酸アミド等が挙げられる。これらの親水性モノマーには、必要に応じて、ヒドロキシ基、カルボキシル基、ポリエーテル基等の親水性基が結合していてもよい。中でも、ヒドロキシエチルアクリルアミド、アクリル酸を好ましく挙げることができる。親水性モノマーとして、ヒドロキシエチルアクリルアミド又はアクリル酸を使用した場合、吸水性シートのシート硬さを調整でき、また、タック性も弱めることができる。その結果、吸水性シートをロールツーロールで製造することが可能となる。
The water-soluble acrylic monomer component may be various hydrophilic monomers in addition to the above-mentioned hydroxyl group-containing acrylic monomer as long as it shows transparency when mixed with 18% by mass or more of water at 23 ° C. There may be. Specific examples of the various hydrophilic monomers include vinyl alcohol, vinyl acetate, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid amide, and the like. A hydrophilic group such as a hydroxy group, a carboxyl group, or a polyether group may be bonded to these hydrophilic monomers as necessary. Of these, hydroxyethylacrylamide and acrylic acid can be preferably mentioned. When hydroxyethyl acrylamide or acrylic acid is used as the hydrophilic monomer, the sheet hardness of the water-absorbent sheet can be adjusted, and tackiness can be weakened. As a result, it becomes possible to manufacture a water-absorbent sheet by roll-to-roll.
また、親水性モノマーとして、以下の式（１）の（メタ）アクリルアミド系第４級アンモニウム塩モノマーを使用することもできる。このモノマーを使用した場合には、本発明の吸水性ポリマーシートに対し高吸水性を付与し、また、含水状態が維持されている吸水性シートにおけるタック性を抑制もしくは調整することができる。
Also, a (meth) acrylamide quaternary ammonium salt monomer represented by the following formula (1) can be used as the hydrophilic monomer. When this monomer is used, high water absorption can be imparted to the water-absorbing polymer sheet of the present invention, and tackiness in the water-absorbing sheet in which the water-containing state is maintained can be suppressed or adjusted.
式（１）中、Ｒ1及びＲ2はそれぞれ独立的に水素原子又は低級アルキル基である。Ｒ3及びＲ4は低級アルキル基であり、Ｒ5は低級アルキル基、低級アルケニル基又はベンジル基であり、Ａは低級アルキレン基であり、X-はハロゲンアニオン又は過塩素酸アニオンである。これらの置換基において、低級アルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、Ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基等が挙げられ、中でもメチル基が好ましい。低級アルケニル基としては、エテニル基、１又は２－プロペニル基、１，２又は３－ブテニル基、１，２，３又は４－ペンテニル基、１，２，３，４又は５－ヘキセニル基等が挙げられる。低級アルキレン基としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基等が挙げられる。ハロゲンアニオンとしては、クロロアニオン、ブロモアニオン、イオドアニオンが挙げられる。
In formula (1), R 1 and R 2 are each independently a hydrogen atom or a lower alkyl group. R 3 and R 4 are a lower alkyl group, R 5 is a lower alkyl group, a lower alkenyl group or a benzyl group, A is a lower alkylene group, and X − is a halogen anion or a perchlorate anion. In these substituents, examples of the lower alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a Sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Of these, a methyl group is preferred. Examples of the lower alkenyl group include ethenyl group, 1 or 2-propenyl group, 1,2 or 3-butenyl group, 1,2,3 or 4-pentenyl group, 1,2,3,4, 5-hexenyl group and the like. Can be mentioned. Examples of the lower alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. Examples of the halogen anion include chloro anion, bromo anion, and iodo anion.
好ましいＲ1は水素原子であり、好ましいＲ2はメチル基であり、好ましいＲ3、Ｒ4及びＲ5はメチル基であり、好ましいＡはプロピレン基であり、好ましいX-はクロロアニオンである。
Preferred R 1 is a hydrogen atom, preferred R 2 is a methyl group, preferred R 3 , R 4 and R 5 are methyl groups, preferred A is a propylene group, and preferred X − is a chloroanion.
一方、（メタ）アクリルアミド系第４級アンモニウム塩モノマーのカチオン部の具体例としては、アクリロイルアミノメチルトリメチルアンモニウム、アクリロイルアミノメチルトリエチルアンモニウム、アクリロイルアミノメチルトリプロピルアンモニウム、アクリロイルアミノエチルトリメチルアンモニウム、アクリロイルアミノプロピルトリメチルアンモニウム、アクリロイルアミノプロピルメチルジエチルアンモニウム、アクリロイルアミノプロピルエチルジメチルアンモニウム、アクリロイルアミノプロピルメチルジプロピルアンモニウム、アクリロイルアミノプロピルトリエチルアンモニウム、アクリロイルアミノプロピルトリプロピルアンモニウム、アクリロイルアミノエチルジメチルベンジルアンモニウム、アクリロイルアミノプロピルジメチルベンジルアンモニウム、アクリロイルアミノプロピルジエチルベンジルアンモニウムなどのアクリルアミド系第４級アンモニウムカチオンが挙げられる。中でも安価な工業的原料を入手しやすい点で、アクリロイルアミノプロピルトリメチルアンモニウム、アクリロイルアミノプロピルジメチルベンジルアンモニウムが好ましい。特に好ましくは、アクリロイルアミノプロピルトリメチルアンモニウムである。
On the other hand, specific examples of the cation moiety of the (meth) acrylamide-based quaternary ammonium salt monomer include acryloylaminomethyltrimethylammonium, acryloylaminomethyltriethylammonium, acryloylaminomethyltripropylammonium, acryloylaminoethyltrimethylammonium, acryloylaminopropyl. Trimethylammonium, acryloylaminopropylmethyldiethylammonium, acryloylaminopropylethyldimethylammonium, acryloylaminopropylmethyldipropylammonium, acryloylaminopropyltriethylammonium, acryloylaminopropyltripropylammonium, acryloylaminoethyldimethylbenzylammonium, acryloyl Mino dimethyl benzyl ammonium, acrylamide-based quaternary ammonium cations, such as acryloyl aminopropyl diethyl benzyl ammonium. Of these, acryloylaminopropyltrimethylammonium and acryloylaminopropyldimethylbenzylammonium are preferred because inexpensive industrial raw materials are easily available. Particularly preferred is acryloylaminopropyltrimethylammonium.
従って、好ましい式（１）の（メタ）アクリルアミド系第４級アンモニウム塩モノマーとしては、アクリロイルアミノプロピルトリメチルアンモニウムクロライド、換言すれば、ジメチルアミノプロピルアクリルアミド塩化メチル塩が挙げられる。
Therefore, preferable (meth) acrylamide type quaternary ammonium salt monomer of the formula (1) includes acryloylaminopropyltrimethylammonium chloride, in other words, dimethylaminopropylacrylamide methyl chloride salt.
（含水アクリル系モノマー膜）
このような水溶性アクリル系モノマー成分と水とを含む含水アクリル系モノマー膜は、後述するように、少なくとも水溶性アクリル系モノマー成分と水とを含有する含水光硬化性アクリル系モノマー組成物をカレンダー法等の常法により成膜したものである。その膜厚は、吸水性シートの用途等により異なるが、通常１０～１０００μｍ、好ましくは５０～５００μｍである。 (Water-containing acrylic monomer film)
Such a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water is obtained by calendering a water-containing photocurable acrylic monomer composition containing at least a water-soluble acrylic monomer component and water as described later. The film is formed by a conventional method such as a method. The film thickness varies depending on the use of the water-absorbent sheet, but is usually 10 to 1000 μm, preferably 50 to 500 μm.
このような水溶性アクリル系モノマー成分と水とを含む含水アクリル系モノマー膜は、後述するように、少なくとも水溶性アクリル系モノマー成分と水とを含有する含水光硬化性アクリル系モノマー組成物をカレンダー法等の常法により成膜したものである。その膜厚は、吸水性シートの用途等により異なるが、通常１０～１０００μｍ、好ましくは５０～５００μｍである。 (Water-containing acrylic monomer film)
Such a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water is obtained by calendering a water-containing photocurable acrylic monomer composition containing at least a water-soluble acrylic monomer component and water as described later. The film is formed by a conventional method such as a method. The film thickness varies depending on the use of the water-absorbent sheet, but is usually 10 to 1000 μm, preferably 50 to 500 μm.
このような含水アクリル系モノマー膜中の含水量は、後述される含水光硬化膜の含水量と略同様となることから、吸水性シートとして求められる機械的強度や製造工程における取り扱い性の観点から調整される。この含水量は、好ましくは５～５０質量％の範囲である。この範囲であれば、水溶性アクリル系モノマー成分が１８質量％以上の水に混和性を示すということと相まって、紫外線照射された後の含水光硬化膜のヘイズ度を確実に低減できるという効果が得られる。なお、水としては、蒸留水、イオン交換水を好ましく使用できる。また、含水量の測定は、加熱秤量による重量変化測定により行うことができる。
Since the water content in such a water-containing acrylic monomer film is substantially the same as the water content of a water-containing photocured film described later, from the viewpoint of mechanical strength required as a water-absorbent sheet and handling in the manufacturing process. Adjusted. The water content is preferably in the range of 5 to 50% by mass. Within this range, coupled with the fact that the water-soluble acrylic monomer component is miscible with 18% by mass or more of water, there is an effect that the haze degree of the water-containing photocured film after being irradiated with ultraviolet rays can be reliably reduced. can get. In addition, as water, distilled water and ion-exchange water can be used preferably. The water content can be measured by measuring a change in weight by heating weighing.
（光重合開始剤・架橋剤）
なお、本発明において、含水アクリル系モノマー膜は、通常、光重合開始剤を含有する。モノマー膜の硬化を促進させるためである。また、含水アクリル系モノマー膜は、更に、架橋剤を含有することが好ましい。その含水光硬化膜の水の保持力を高めると共に含水光硬化膜をロールツーロールで巻き取ることを可能とする機械的強度を含水光硬化膜に付与するためである。 (Photopolymerization initiator / crosslinking agent)
In the present invention, the water-containing acrylic monomer film usually contains a photopolymerization initiator. This is to accelerate the curing of the monomer film. Moreover, it is preferable that a water-containing acrylic monomer film | membrane contains a crosslinking agent further. This is to increase the water holding power of the water-containing photocured film and to impart mechanical strength to the water-containing photocured film that enables the water-containing photocured film to be wound up by roll-to-roll.
なお、本発明において、含水アクリル系モノマー膜は、通常、光重合開始剤を含有する。モノマー膜の硬化を促進させるためである。また、含水アクリル系モノマー膜は、更に、架橋剤を含有することが好ましい。その含水光硬化膜の水の保持力を高めると共に含水光硬化膜をロールツーロールで巻き取ることを可能とする機械的強度を含水光硬化膜に付与するためである。 (Photopolymerization initiator / crosslinking agent)
In the present invention, the water-containing acrylic monomer film usually contains a photopolymerization initiator. This is to accelerate the curing of the monomer film. Moreover, it is preferable that a water-containing acrylic monomer film | membrane contains a crosslinking agent further. This is to increase the water holding power of the water-containing photocured film and to impart mechanical strength to the water-containing photocured film that enables the water-containing photocured film to be wound up by roll-to-roll.
光重合開始剤としては、公知のラジカル型光重合開始剤を採用することができる。具体的には、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、アニソールメチルエーテルなどのベンゾイン類、４－（２－ヒドロキシエトキシ）フェニル（２－ヒドロキシ－２－プロピル）ケトン（ダロキュアー２９５９；ＢＡＳＦジャパン（株））、α－ヒドロキシ－α、α'－ジメチルアセトフェノン（ダロキュアー１１７３；ＢＡＳＦジャパン（株））、メトキシアセトフェノン、２，２'－ジメトキシ－２－フェニルアセトフェノン（イルガキュアー６５１；ＢＡＳＦジャパン（株））、２－ヒドロキシ－２－シクロヘキシルアセトフェノン（イルガキュアー１８４；ＢＡＳＦジャパン（株））、２，２－ジエトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、４－フェノキシジクロロアセトフェノン、４－ｔ－ブチル－ジクロロアセトフェノンなどのアセトフェノン類、２－ヒドロキシ－２－メチルプロピオフェノン、２－ヒドロキシ－４'－イソプロピル－２－メチルプロピオフェノンなどのプロピオフェノン類、ベンゾフェノン、メチルベンゾフェノン、ｐ－クロルベンゾフェノン、ｐ－ジメチルアミノベンゾフェノンなどのベンゾフェノン類、チオキサントン、２－クロルチオキサントン、２－エチルチオキサントン、２－イソプロピルチオキサントン、２，４－ジクロロチオキサントン、２，４－ジエチルチオキサントン、２，４－ジイソプロピルチオキサントン、ドデシルチオキサントンなどのチオキサントン類、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－２，４－ジ－ｎ－ブトキシフェニルフォスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルフェニルフォスフィンオキサイドなどのアシルフォスフィンオキサイド類、ベンジル、ジベンゾスベロン、α－アシルオキシムエステルなどが挙げられる。
As the photopolymerization initiator, a known radical photopolymerization initiator can be employed. Specifically, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and anisole methyl ether, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone (Darocur 2959; BASF Japan Ltd.), α-hydroxy-α, α′-dimethylacetophenone (Darocur 1173; BASF Japan Ltd.), methoxyacetophenone, 2,2′-dimethoxy-2-phenylacetophenone (Irgacure) 651; BASF Japan K.K.), 2-hydroxy-2-cyclohexylacetophenone (Irgacure 184; BASF Japan K.K.), 2,2-diethoxyacetophenone, 2,2-di- Acetophenones such as toxi-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4 ′ -Propiophenones such as isopropyl-2-methylpropiophenone, benzophenones such as benzophenone, methylbenzophenone, p-chlorobenzophenone, p-dimethylaminobenzophenone, thioxanthone, 2-chlorothioxanthone, 2-ethylthioxanthone, 2- Thio such as isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone Sandtons, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-di-n -Acylphosphine oxides such as butoxyphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphenylphosphine oxide, benzyl, dibenzosuberone, α-acyloxime esters, etc. Can be mentioned.
また、架橋剤としては、公知の架橋剤を採用することができ、好ましくは多官能アクリレート系架橋剤を使用することができる。具体的には、トリプロピレングリコールジアクリレート、ペンタエリスリトールトリアクリレート、トリメチロールプロパントリアクリレート、イソシアヌル酸ＥＯ変性ジ及びトリアクリレート、トリメチロールプロパンＥＯ変成トリアクリレート、ジペンタエリスリトールペンタ及びヘキサアクリレート、ジトリメチロールプロパンテトラアクリレート等を挙げることができる。
As the crosslinking agent, a known crosslinking agent can be employed, and a polyfunctional acrylate-based crosslinking agent can be preferably used. Specifically, tripropylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, isocyanuric acid EO-modified di- and triacrylate, trimethylolpropane EO-modified triacrylate, dipentaerythritol penta- and hexaacrylate, ditrimethylolpropane Examples thereof include tetraacrylate.
含水アクリル系モノマー膜における光重合開始剤の配合量は、上述した水溶性アクリル系モノマー成分１００質量部に対し、好ましくは０．０１～１質量部、より好ましくは０．１～０．５質量部である。この範囲であれば、良好な成膜性を実現することができる。また、含水アクリル系モノマー膜における架橋剤の配合量は、上述した水溶性アクリル系モノマー成分１００質量部に対し、好ましくは０．０１～５質量部、より好ましくは０．１～１質量部である。この範囲であれば、良好な吸水性と耐溶解性とを実現できる。
The blending amount of the photopolymerization initiator in the water-containing acrylic monomer film is preferably 0.01 to 1 part by mass, more preferably 0.1 to 0.5 part by mass with respect to 100 parts by mass of the water-soluble acrylic monomer component described above. Part. If it is this range, favorable film formability is realizable. Further, the blending amount of the crosslinking agent in the water-containing acrylic monomer film is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the water-soluble acrylic monomer component described above. is there. Within this range, good water absorption and dissolution resistance can be realized.
（含水光硬化膜）
本発明の吸水性シートは、上述した含水アクリル系モノマー膜に由来する含水光硬化膜を含有する。含水アクリル系モノマー膜の光硬化は、後述するように、含水アクリル系モノマー膜への紫外線照射により行うことができる。その膜厚は、吸水性シートの用途等により異なるが、通常１０～１０００μｍ、好ましくは５０～５００μｍである。 (Water-containing photocured film)
The water absorbent sheet of the present invention contains a water-containing photocured film derived from the water-containing acrylic monomer film described above. The photo-curing of the water-containing acrylic monomer film can be performed by irradiating the water-containing acrylic monomer film with ultraviolet rays as will be described later. The film thickness varies depending on the use of the water-absorbent sheet, but is usually 10 to 1000 μm, preferably 50 to 500 μm.
本発明の吸水性シートは、上述した含水アクリル系モノマー膜に由来する含水光硬化膜を含有する。含水アクリル系モノマー膜の光硬化は、後述するように、含水アクリル系モノマー膜への紫外線照射により行うことができる。その膜厚は、吸水性シートの用途等により異なるが、通常１０～１０００μｍ、好ましくは５０～５００μｍである。 (Water-containing photocured film)
The water absorbent sheet of the present invention contains a water-containing photocured film derived from the water-containing acrylic monomer film described above. The photo-curing of the water-containing acrylic monomer film can be performed by irradiating the water-containing acrylic monomer film with ultraviolet rays as will be described later. The film thickness varies depending on the use of the water-absorbent sheet, but is usually 10 to 1000 μm, preferably 50 to 500 μm.
含水光硬化膜の含水量は、含水アクリル系モノマー膜の含水量に依存するが、好ましくは５～５０質量％、より好ましくは１０～３０質量％である。この範囲であれば、良好な成膜性を実現することができる。含水光硬化膜の含水量の測定は、含水アクリル系モノマー膜の含水量の測定と同様の手法により測定できる。
The water content of the water-containing photocured film depends on the water content of the water-containing acrylic monomer film, but is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. If it is this range, favorable film formability is realizable. The water content of the water-containing photocured film can be measured by the same method as the measurement of the water content of the water-containing acrylic monomer film.
含水光硬化膜のＪＩＳ Ｋ７１３６に準拠するヘイズ度は、好ましくは８％以下、より好ましくは５％以下である。この範囲であれば、良好な透明性を実現できる。
The haze degree of the hydrous photocured film according to JIS K7136 is preferably 8% or less, more preferably 5% or less. If it is this range, favorable transparency is realizable.
含水光硬化膜の吸水性は、自重に対して好ましくは１０質量％以上、より好ましくは５０質量％以上である。この範囲であれば、結露防止等を実現できる。
The water absorption of the water-containing photocured film is preferably 10% by mass or more, more preferably 50% by mass or more based on its own weight. If it is this range, dew condensation prevention etc. are realizable.
（その他の成分）
本発明の吸水性シートの含水光硬化膜は、本発明の効果を損なわない範囲で、含水光硬化膜に相溶する透明な熱可塑性樹脂や、酸化防止剤、光安定剤、重合禁止剤、シランカップリング剤、染料等を含有することができる。 (Other ingredients)
The water-containing photocured film of the water-absorbent sheet of the present invention is a transparent thermoplastic resin compatible with the water-containing photocured film, an antioxidant, a light stabilizer, a polymerization inhibitor, as long as the effects of the present invention are not impaired. Silane coupling agents, dyes and the like can be contained.
本発明の吸水性シートの含水光硬化膜は、本発明の効果を損なわない範囲で、含水光硬化膜に相溶する透明な熱可塑性樹脂や、酸化防止剤、光安定剤、重合禁止剤、シランカップリング剤、染料等を含有することができる。 (Other ingredients)
The water-containing photocured film of the water-absorbent sheet of the present invention is a transparent thermoplastic resin compatible with the water-containing photocured film, an antioxidant, a light stabilizer, a polymerization inhibitor, as long as the effects of the present invention are not impaired. Silane coupling agents, dyes and the like can be contained.
（吸水性シートの製造方法）
水溶性アクリル系モノマー成分と水とを含有する含水アクリル系モノマー膜の含水光硬化膜を有する本発明の吸水性シートは、以下の工程（Ａ）～（Ｃ）を有する製造方法により製造することができる。 (Method for producing water-absorbent sheet)
The water absorbent sheet of the present invention having a water-containing photocured film of a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water should be produced by a production method having the following steps (A) to (C). Can do.
水溶性アクリル系モノマー成分と水とを含有する含水アクリル系モノマー膜の含水光硬化膜を有する本発明の吸水性シートは、以下の工程（Ａ）～（Ｃ）を有する製造方法により製造することができる。 (Method for producing water-absorbent sheet)
The water absorbent sheet of the present invention having a water-containing photocured film of a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water should be produced by a production method having the following steps (A) to (C). Can do.
（工程Ａ）
まず、含水光硬化性アクリル系モノマー組成物をベースフィルムに成膜することにより含水アクリル系モノマー膜を形成する。この含水アクリル系モノマー膜の形成は、公知の手法を利用して形成することができる。例えば、剥離処理されたポリエチレンテレフタレートフィルムなどのベースフィルムに、含水光硬化性アクリル系モノマー組成物を公知の手法、例えばカレンダー法やバーコータ法等により塗布することにより行うことができる。また、ベースフィルムは、後述する工程Ｃにおける紫外線照射が可能となるように透明（紫外線透過性）であることが好ましい。 (Process A)
First, a water-containing acrylic monomer film is formed by forming a water-containing photocurable acrylic monomer composition on a base film. The water-containing acrylic monomer film can be formed using a known method. For example, it can be performed by applying a water-containing photocurable acrylic monomer composition to a base film such as a polyethylene terephthalate film subjected to a release treatment by a known method such as a calendar method or a bar coater method. Moreover, it is preferable that the base film is transparent (ultraviolet ray transmissive) so that the ultraviolet ray can be irradiated in the step C described later.
まず、含水光硬化性アクリル系モノマー組成物をベースフィルムに成膜することにより含水アクリル系モノマー膜を形成する。この含水アクリル系モノマー膜の形成は、公知の手法を利用して形成することができる。例えば、剥離処理されたポリエチレンテレフタレートフィルムなどのベースフィルムに、含水光硬化性アクリル系モノマー組成物を公知の手法、例えばカレンダー法やバーコータ法等により塗布することにより行うことができる。また、ベースフィルムは、後述する工程Ｃにおける紫外線照射が可能となるように透明（紫外線透過性）であることが好ましい。 (Process A)
First, a water-containing acrylic monomer film is formed by forming a water-containing photocurable acrylic monomer composition on a base film. The water-containing acrylic monomer film can be formed using a known method. For example, it can be performed by applying a water-containing photocurable acrylic monomer composition to a base film such as a polyethylene terephthalate film subjected to a release treatment by a known method such as a calendar method or a bar coater method. Moreover, it is preferable that the base film is transparent (ultraviolet ray transmissive) so that the ultraviolet ray can be irradiated in the step C described later.
含水光硬化性アクリル系モノマー組成物は、水溶性アクリル系モノマー成分と、光重合開始剤と、架橋剤と、水とを含有する。これらの成分の種類や配合割合については、本発明の吸水性シートに関連して説明したとおりである。
The water-containing photocurable acrylic monomer composition contains a water-soluble acrylic monomer component, a photopolymerization initiator, a crosslinking agent, and water. The types and blending ratios of these components are as described in relation to the water absorbent sheet of the present invention.
即ち、水溶性アクリル系モノマー成分としては、２３℃で１８質量％以上の水と混和したときに透明性を示すもの、具体的にはＪＩＳ Ｋ７１３６に準拠したヘイズ度が８％以下のものを使用する。含水アクリル系モノマー膜を光硬化させて含水光硬化膜とした際に良好な透明性を実現するためである。
That is, as the water-soluble acrylic monomer component, one that exhibits transparency when mixed with 18% by mass or more of water at 23 ° C., specifically, one having a haze degree of 8% or less according to JIS K7136 is used. To do. This is for realizing good transparency when the water-containing acrylic monomer film is photocured to form a water-containing photocured film.
なお、含水光硬化性アクリル系モノマー組成物は、光硬化させた後の含水光硬化膜に相溶する透明な熱可塑性樹脂や、酸化防止剤、光安定剤、重合禁止剤、シランカップリング剤、染料等を含有することができる。
The water-containing photocurable acrylic monomer composition is a transparent thermoplastic resin that is compatible with the water-containing photocured film after photocuring, an antioxidant, a light stabilizer, a polymerization inhibitor, and a silane coupling agent. , Dyes and the like can be contained.
（工程Ｂ）
次に、含水アクリル系モノマー膜に透明剥離フィルムを積層する。このフィルムの積層により、以下の工程Ｃにおいて含水アクリル系モノマー膜の含水量を保持したまま光硬化させることができる。透明剥離フィルムとしては、公知の透明剥離フィルムを使用することができる、例えば、市販の剥離処理したポリエチレンテレフタレートフィルム等を使用することができる。なお、透明剥離フィルムの「透明」とは、後述の工程Ｃで使用する紫外線が透過するという意味である。 (Process B)
Next, a transparent release film is laminated on the water-containing acrylic monomer film. By laminating this film, it can be photocured while maintaining the water content of the water-containing acrylic monomer film in the following step C. As the transparent release film, a known transparent release film can be used. For example, a commercially available release-treated polyethylene terephthalate film or the like can be used. The “transparent” of the transparent release film means that the ultraviolet rays used in Step C described later are transmitted.
次に、含水アクリル系モノマー膜に透明剥離フィルムを積層する。このフィルムの積層により、以下の工程Ｃにおいて含水アクリル系モノマー膜の含水量を保持したまま光硬化させることができる。透明剥離フィルムとしては、公知の透明剥離フィルムを使用することができる、例えば、市販の剥離処理したポリエチレンテレフタレートフィルム等を使用することができる。なお、透明剥離フィルムの「透明」とは、後述の工程Ｃで使用する紫外線が透過するという意味である。 (Process B)
Next, a transparent release film is laminated on the water-containing acrylic monomer film. By laminating this film, it can be photocured while maintaining the water content of the water-containing acrylic monomer film in the following step C. As the transparent release film, a known transparent release film can be used. For example, a commercially available release-treated polyethylene terephthalate film or the like can be used. The “transparent” of the transparent release film means that the ultraviolet rays used in Step C described later are transmitted.
（工程Ｃ）
含水アクリル系モノマー膜に対し、透明剥離フィルム若しくはベースフィルム側から紫外線を照射することにより、含水アクリル系モノマー膜の含水量を保持したまま含水光硬化膜を形成する。紫外線の照射は、公知の紫外線照射技術を適用して行うことができる。例えば、透明剥離フィルム若しくはベースフィルム側から、含水アクリル系モノマー膜に対し、ケミカルランプ、高圧水銀ランプ等が発した紫外線を照射することにより行うことができる。紫外線の照射条件の一例としては、０．５～１．５ｍＷ／ｃｍ2に調整されたケミカルランプで５～１０分間紫外線を照射し、続いて、高圧水銀ランプで１０００～１５００ｍＪ／ｃｍ2の光量で照射することが挙げられる。なお、含水アクリル系モノマー膜の含水量を「保持したまま」とは、紫外線照射前の含水アクリル系モノマー膜に含まれている水分量と、紫外線照射後の含水光硬化膜に含まれる水分量とが実質的に同量であることを意味する。また、含水アクリル系モノマー膜の含水量を保持したままであるか否かは、含水アクリル系モノマー膜の含水量の公知の測定手法と同様の手法により評価することができる。 (Process C)
By irradiating the water-containing acrylic monomer film with ultraviolet rays from the transparent release film or the base film side, a water-containing photocured film is formed while maintaining the water content of the water-containing acrylic monomer film. Ultraviolet irradiation can be performed by applying a known ultraviolet irradiation technique. For example, it can be carried out by irradiating the water-containing acrylic monomer film with ultraviolet rays emitted from a chemical lamp, a high-pressure mercury lamp or the like from the transparent release film or base film side. As an example of the irradiation condition of the ultraviolet ray, the chemical lamp adjusted to 0.5 to 1.5 mW / cm 2 is irradiated with the ultraviolet ray for 5 to 10 minutes, and then, the light intensity of 1000 to 1500 mJ / cm 2 with the high pressure mercury lamp. And irradiation. In addition, the water content of the hydrated acrylic monomer film is “maintained” means that the moisture content contained in the hydrated acrylic monomer film before the ultraviolet irradiation and the moisture content contained in the hydrated photocured film after the ultraviolet irradiation. Means substantially the same amount. Further, whether or not the water content of the water-containing acrylic monomer film is maintained can be evaluated by a method similar to a known method for measuring the water content of the water-containing acrylic monomer film.
含水アクリル系モノマー膜に対し、透明剥離フィルム若しくはベースフィルム側から紫外線を照射することにより、含水アクリル系モノマー膜の含水量を保持したまま含水光硬化膜を形成する。紫外線の照射は、公知の紫外線照射技術を適用して行うことができる。例えば、透明剥離フィルム若しくはベースフィルム側から、含水アクリル系モノマー膜に対し、ケミカルランプ、高圧水銀ランプ等が発した紫外線を照射することにより行うことができる。紫外線の照射条件の一例としては、０．５～１．５ｍＷ／ｃｍ2に調整されたケミカルランプで５～１０分間紫外線を照射し、続いて、高圧水銀ランプで１０００～１５００ｍＪ／ｃｍ2の光量で照射することが挙げられる。なお、含水アクリル系モノマー膜の含水量を「保持したまま」とは、紫外線照射前の含水アクリル系モノマー膜に含まれている水分量と、紫外線照射後の含水光硬化膜に含まれる水分量とが実質的に同量であることを意味する。また、含水アクリル系モノマー膜の含水量を保持したままであるか否かは、含水アクリル系モノマー膜の含水量の公知の測定手法と同様の手法により評価することができる。 (Process C)
By irradiating the water-containing acrylic monomer film with ultraviolet rays from the transparent release film or the base film side, a water-containing photocured film is formed while maintaining the water content of the water-containing acrylic monomer film. Ultraviolet irradiation can be performed by applying a known ultraviolet irradiation technique. For example, it can be carried out by irradiating the water-containing acrylic monomer film with ultraviolet rays emitted from a chemical lamp, a high-pressure mercury lamp or the like from the transparent release film or base film side. As an example of the irradiation condition of the ultraviolet ray, the chemical lamp adjusted to 0.5 to 1.5 mW / cm 2 is irradiated with the ultraviolet ray for 5 to 10 minutes, and then, the light intensity of 1000 to 1500 mJ / cm 2 with the high pressure mercury lamp. And irradiation. In addition, the water content of the hydrated acrylic monomer film is “maintained” means that the moisture content contained in the hydrated acrylic monomer film before the ultraviolet irradiation and the moisture content contained in the hydrated photocured film after the ultraviolet irradiation. Means substantially the same amount. Further, whether or not the water content of the water-containing acrylic monomer film is maintained can be evaluated by a method similar to a known method for measuring the water content of the water-containing acrylic monomer film.
このように作成された含水光硬化膜を有する吸水性シートは、透明剥離フィルムを取り除き、透明ディスプレイ等の被着物に貼り付けて好ましく使用することができる。
The water-absorbent sheet having a water-containing photocured film thus prepared can be preferably used by removing the transparent release film and attaching it to an adherend such as a transparent display.
以下、本発明を実験例並びに実施例により具体的に説明する。
Hereinafter, the present invention will be specifically described with reference to experimental examples and examples.
実験例（アクリル系モノマーと水との混和試験）
アクリル系モノマーと水とを、２３℃で様々な割合で均一に混合した時の混合液の状態を目視にて観察し、無色透明な場合を良好「〇」と評価し、白濁している場合を不良「×」と評価した。得られた結果を表１に示す。なお、「良好」及び「不良」という評価は、ＪＩＳ Ｋ７１３６に準拠するヘイズ度でそれぞれ「８％以下」及び「８％超」の場合に該当すると考えられる。 Experimental example (mixing test of acrylic monomer and water)
When the acrylic monomer and water are uniformly mixed in various proportions at 23 ° C, the state of the liquid mixture is visually observed. Was evaluated as defective “x”. The obtained results are shown in Table 1. It should be noted that the evaluations of “good” and “bad” correspond to cases where the haze degree according to JIS K7136 is “less than 8%” and “greater than 8%”, respectively.
アクリル系モノマーと水とを、２３℃で様々な割合で均一に混合した時の混合液の状態を目視にて観察し、無色透明な場合を良好「〇」と評価し、白濁している場合を不良「×」と評価した。得られた結果を表１に示す。なお、「良好」及び「不良」という評価は、ＪＩＳ Ｋ７１３６に準拠するヘイズ度でそれぞれ「８％以下」及び「８％超」の場合に該当すると考えられる。 Experimental example (mixing test of acrylic monomer and water)
When the acrylic monomer and water are uniformly mixed in various proportions at 23 ° C, the state of the liquid mixture is visually observed. Was evaluated as defective “x”. The obtained results are shown in Table 1. It should be noted that the evaluations of “good” and “bad” correspond to cases where the haze degree according to JIS K7136 is “less than 8%” and “greater than 8%”, respectively.
表１から、２－ヒドロキシブチルアクリレートは２３℃で水を１８質量部以上混合すると白濁し、他のアクリレート系モノマーは、２３℃で水を１８質量部以上混合しても白濁しないことがわかる。従って、含水状態でアクリル系モノマー組成物を光硬化させる場合には、少なくとも２３℃で水を１８質量部以上混合しても白濁しない水溶性アクリル系モノマーを使用すべきであることが理解される。
From Table 1, it can be seen that 2-hydroxybutyl acrylate becomes cloudy when mixed with 18 parts by mass or more of water at 23 ° C., and other acrylate monomers do not become cloudy even when mixed with 18 parts or more of water at 23 ° C. Accordingly, it is understood that when the acrylic monomer composition is photocured in a water-containing state, a water-soluble acrylic monomer that does not become cloudy even when mixed with 18 parts by mass or more of water at 23 ° C. should be used. .
実施例１～３、比較例１
表２に示したアクリル系モノマー８８質量部、水１２質量部、光重合開始剤（ダロキュアー１１７３、ＢＡＳＦジャパン（株））０．３質量部、及び架橋剤（Ｍー４００、東亞合成（株））０．３質量部を回転翼式撹拌機（スリーワンモーター、新東科学（株））を用いて均一に混合して、含水光硬化性アクリル系モノマー組成物を調製した。この含水光硬化性アクリル系モノマー組成物を、バーコータを用いて剥離処理ポリエチレンテレフタレートフィルムに２００μｍ厚で塗布し、その上に別の剥離処理ポリエチレンテレフタレートフィルムを載置した。２枚の剥離処理ポリエチレンテレフタレートフィルムに挟持された含水光硬化性アクリル系モノマー組成物の膜（すなわち、含水アクリル系モノマー膜）に対し、１ｍＷ／ｃｍ2に調整したケミカルランプから紫外線（主波長３６５ｎｍ）を５分間照射し、続いて高圧水銀ランプから紫外線（主波長３６５ｎｍ）を１０００ｍＪ／ｃｍ2の積算光量となるように照射することにより、含水光硬化膜が剥離処理ポリエチレンテレフタレートに挟持されている吸水性シートを作成した。なお、実施例１～３並びに比較例１の吸水性シートにおける含水光硬化性アクリル系モノマー組成物膜の含水量と、その硬化した含水光硬化膜の含水量とは、いずれもほぼ１２％（質量基準）であり、実質的な差はなかった。 Examples 1 to 3, Comparative Example 1
88 parts by mass of acrylic monomers shown in Table 2, 12 parts by mass of water, 0.3 parts by mass of a photopolymerization initiator (Darocur 1173, BASF Japan Ltd.), and a crosslinking agent (M-400, Toagosei Co., Ltd.) ) 0.3 parts by mass was uniformly mixed using a rotary blade stirrer (Three-One Motor, Shinto Kagaku Co., Ltd.) to prepare a water-containing photocurable acrylic monomer composition. This water-containing photocurable acrylic monomer composition was applied to a release-treated polyethylene terephthalate film with a thickness of 200 μm using a bar coater, and another release-treated polyethylene terephthalate film was placed thereon. UV light (main wavelength: 365 nm) from a chemical lamp adjusted to 1 mW / cm 2 with respect to a film of a water-containing photocurable acrylic monomer composition sandwiched between two release-treated polyethylene terephthalate films (that is, a water-containing acrylic monomer film) ) For 5 minutes, followed by irradiation with ultraviolet light (main wavelength 365 nm) from a high-pressure mercury lamp so as to obtain an integrated light quantity of 1000 mJ / cm 2 , the water-containing photocured film is sandwiched between the release-treated polyethylene terephthalate. A water absorbent sheet was prepared. Note that the water content of the water-containing photocurable acrylic monomer composition film in the water-absorbent sheets of Examples 1 to 3 and Comparative Example 1 and the water content of the cured water-containing photocured film were both approximately 12% ( Mass basis) and there was no substantial difference.
表２に示したアクリル系モノマー８８質量部、水１２質量部、光重合開始剤（ダロキュアー１１７３、ＢＡＳＦジャパン（株））０．３質量部、及び架橋剤（Ｍー４００、東亞合成（株））０．３質量部を回転翼式撹拌機（スリーワンモーター、新東科学（株））を用いて均一に混合して、含水光硬化性アクリル系モノマー組成物を調製した。この含水光硬化性アクリル系モノマー組成物を、バーコータを用いて剥離処理ポリエチレンテレフタレートフィルムに２００μｍ厚で塗布し、その上に別の剥離処理ポリエチレンテレフタレートフィルムを載置した。２枚の剥離処理ポリエチレンテレフタレートフィルムに挟持された含水光硬化性アクリル系モノマー組成物の膜（すなわち、含水アクリル系モノマー膜）に対し、１ｍＷ／ｃｍ2に調整したケミカルランプから紫外線（主波長３６５ｎｍ）を５分間照射し、続いて高圧水銀ランプから紫外線（主波長３６５ｎｍ）を１０００ｍＪ／ｃｍ2の積算光量となるように照射することにより、含水光硬化膜が剥離処理ポリエチレンテレフタレートに挟持されている吸水性シートを作成した。なお、実施例１～３並びに比較例１の吸水性シートにおける含水光硬化性アクリル系モノマー組成物膜の含水量と、その硬化した含水光硬化膜の含水量とは、いずれもほぼ１２％（質量基準）であり、実質的な差はなかった。 Examples 1 to 3, Comparative Example 1
88 parts by mass of acrylic monomers shown in Table 2, 12 parts by mass of water, 0.3 parts by mass of a photopolymerization initiator (Darocur 1173, BASF Japan Ltd.), and a crosslinking agent (M-400, Toagosei Co., Ltd.) ) 0.3 parts by mass was uniformly mixed using a rotary blade stirrer (Three-One Motor, Shinto Kagaku Co., Ltd.) to prepare a water-containing photocurable acrylic monomer composition. This water-containing photocurable acrylic monomer composition was applied to a release-treated polyethylene terephthalate film with a thickness of 200 μm using a bar coater, and another release-treated polyethylene terephthalate film was placed thereon. UV light (main wavelength: 365 nm) from a chemical lamp adjusted to 1 mW / cm 2 with respect to a film of a water-containing photocurable acrylic monomer composition sandwiched between two release-treated polyethylene terephthalate films (that is, a water-containing acrylic monomer film) ) For 5 minutes, followed by irradiation with ultraviolet light (main wavelength 365 nm) from a high-pressure mercury lamp so as to obtain an integrated light quantity of 1000 mJ / cm 2 , the water-containing photocured film is sandwiched between the release-treated polyethylene terephthalate. A water absorbent sheet was prepared. Note that the water content of the water-containing photocurable acrylic monomer composition film in the water-absorbent sheets of Examples 1 to 3 and Comparative Example 1 and the water content of the cured water-containing photocured film were both approximately 12% ( Mass basis) and there was no substantial difference.
＜評価＞
含水光硬化性アクリル系モノマー組成物の「透明性」を以下に説明するように評価し、また、得られた吸水性シートの「吸水性」について、以下に説明するように「吸水率」を試験し、評価した。加えて、吸水性シート（含水光硬化膜）の「透明性」について、以下に説明するようにへイズ度を測定し評価した。得られた結果を表２に示す。 <Evaluation>
The “transparency” of the water-containing photocurable acrylic monomer composition is evaluated as described below, and the “water absorption” of the obtained water absorbent sheet is set to “water absorption” as described below. Tested and evaluated. In addition, the “transparency” of the water-absorbent sheet (water-containing photocured film) was evaluated by measuring the degree of haze as described below. The obtained results are shown in Table 2.
含水光硬化性アクリル系モノマー組成物の「透明性」を以下に説明するように評価し、また、得られた吸水性シートの「吸水性」について、以下に説明するように「吸水率」を試験し、評価した。加えて、吸水性シート（含水光硬化膜）の「透明性」について、以下に説明するようにへイズ度を測定し評価した。得られた結果を表２に示す。 <Evaluation>
The “transparency” of the water-containing photocurable acrylic monomer composition is evaluated as described below, and the “water absorption” of the obtained water absorbent sheet is set to “water absorption” as described below. Tested and evaluated. In addition, the “transparency” of the water-absorbent sheet (water-containing photocured film) was evaluated by measuring the degree of haze as described below. The obtained results are shown in Table 2.
（含水光硬化性アクリル系モノマー組成物の透明性）
組成物の状態を目視にて観察し、無色透明な場合を良好「〇」と評価し、白濁している場合を不良「×」と評価した。 (Transparency of water-containing photocurable acrylic monomer composition)
The state of the composition was visually observed, and the case where it was colorless and transparent was evaluated as good “◯”, and the case where it was cloudy was evaluated as defective “×”.
組成物の状態を目視にて観察し、無色透明な場合を良好「〇」と評価し、白濁している場合を不良「×」と評価した。 (Transparency of water-containing photocurable acrylic monomer composition)
The state of the composition was visually observed, and the case where it was colorless and transparent was evaluated as good “◯”, and the case where it was cloudy was evaluated as defective “×”.
（吸水性シートの吸水性）
吸水性シートを１ｃｍ角に切り出し、両面の剥離処理ポリエチレンテレフタレートフィルムを剥がしたものを、精製水３０ｍｌ中に２４時間浸漬し、浸漬前後のフィルム質量（浸漬前の質量をＷ０、浸漬後の質量をＷ１）を測定し、式「吸水率（％）＝[（Ｗ１－Ｗ０）／Ｗ０]×１００」に従って吸水率を求めた。 (Water absorption of water absorbent sheet)
A water-absorbing sheet was cut into 1 cm square, and both sides of the release-treated polyethylene terephthalate film were immersed in 30 ml of purified water for 24 hours, and the film mass before and after immersion (the mass before immersion was W0, the mass after immersion was W1) was measured, and the water absorption was determined according to the formula “Water absorption (%) = [(W1−W0) / W0] × 100”.
吸水性シートを１ｃｍ角に切り出し、両面の剥離処理ポリエチレンテレフタレートフィルムを剥がしたものを、精製水３０ｍｌ中に２４時間浸漬し、浸漬前後のフィルム質量（浸漬前の質量をＷ０、浸漬後の質量をＷ１）を測定し、式「吸水率（％）＝[（Ｗ１－Ｗ０）／Ｗ０]×１００」に従って吸水率を求めた。 (Water absorption of water absorbent sheet)
A water-absorbing sheet was cut into 1 cm square, and both sides of the release-treated polyethylene terephthalate film were immersed in 30 ml of purified water for 24 hours, and the film mass before and after immersion (the mass before immersion was W0, the mass after immersion was W1) was measured, and the water absorption was determined according to the formula “Water absorption (%) = [(W1−W0) / W0] × 100”.
（吸水性シート（光硬化膜）の透明性）
両面の剥離処理ポリエチレンテレフタレートフィルムを剥がした吸水性シートのヘイズ度を、ＪＩＳ Ｋ７１３６に準拠して測定し、以下の評価基準に従って評価した。 (Transparency of water-absorbent sheet (photocured film))
The haze degree of the water-absorbent sheet from which the release-treated polyethylene terephthalate film on both sides was peeled was measured according to JIS K7136 and evaluated according to the following evaluation criteria.
両面の剥離処理ポリエチレンテレフタレートフィルムを剥がした吸水性シートのヘイズ度を、ＪＩＳ Ｋ７１３６に準拠して測定し、以下の評価基準に従って評価した。 (Transparency of water-absorbent sheet (photocured film))
The haze degree of the water-absorbent sheet from which the release-treated polyethylene terephthalate film on both sides was peeled was measured according to JIS K7136 and evaluated according to the following evaluation criteria.
評価基準
○： ヘイズ度が８％以下である場合
△： ヘイズ度が８％超１０％以下である場合
×： ヘイズ度が１０％超である場合 Evaluation criteria ○: When the haze degree is 8% or less Δ: When the haze degree is more than 8% and 10% or less ×: When the haze degree is more than 10%
○： ヘイズ度が８％以下である場合
△： ヘイズ度が８％超１０％以下である場合
×： ヘイズ度が１０％超である場合 Evaluation criteria ○: When the haze degree is 8% or less Δ: When the haze degree is more than 8% and 10% or less ×: When the haze degree is more than 10%
表２から分かるように、実施例１～３の吸水性シートは、透明性に優れ、しかも良好な吸水性を示していた。特に、水溶性アクリル系モノマーの種類を変更することにより吸水性シートの吸水率をコントロールできることがわかる。
As can be seen from Table 2, the water-absorbent sheets of Examples 1 to 3 were excellent in transparency and exhibited good water absorption. In particular, it can be seen that the water absorption rate of the water absorbent sheet can be controlled by changing the type of the water-soluble acrylic monomer.
それに対し、比較例１の吸水性シートは、水溶性アクリル系モノマーとして、表１に示すように、２３℃で水を１８質量部以上混合すると白濁してしまう２－ヒドロキシブチルアクリレートを使用していたので、吸水性シートの透明性に問題が生じた。
In contrast, the water-absorbent sheet of Comparative Example 1 uses 2-hydroxybutyl acrylate as a water-soluble acrylic monomer, as shown in Table 1, which becomes cloudy when mixed with 18 parts by mass of water at 23 ° C. Therefore, a problem occurred in the transparency of the water absorbent sheet.
本発明の吸水性シートは、良好な吸水性を示し、しかも良好な透明性、具体的には８％以下のヘイズ度を示す。従って、窓ガラスや透明ディスプレイ等に適用する吸水性材料として有用である。
The water-absorbent sheet of the present invention exhibits good water absorption, and also exhibits good transparency, specifically a haze degree of 8% or less. Therefore, it is useful as a water-absorbing material applied to window glass, transparent displays and the like.
Claims (18)
- 水溶性アクリル系モノマー成分と水とを含有する含水アクリル系モノマー膜の含水光硬化膜を有する吸水性シートであって、
水溶性アクリル系モノマー成分が、２３℃で１８質量％以上の水と混和したときに透明性を示すものであることを特徴とする吸水性シート。 A water absorbent sheet having a water-containing photocured film of a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water,
A water-absorbent sheet, wherein the water-soluble acrylic monomer component exhibits transparency when mixed with 18% by mass or more of water at 23 ° C. - ２３℃で１８質量％以上の水と混和したときの水溶性アクリル系モノマー成分の透明性が、へイズ度８％以下である請求項１記載の吸水性シート。 The water-absorbent sheet according to claim 1, wherein the water-soluble acrylic monomer component has a haze of 8% or less when mixed with 18% by mass or more of water at 23 ° C.
- 水溶性アクリル系モノマー成分を構成するすべての水溶性アクリル系モノマーが、２３℃で１８質量％以上の水と混和しても透明性を示すものである請求項１又は２記載の吸水性シート。 The water-absorbent sheet according to claim 1 or 2, wherein all water-soluble acrylic monomers constituting the water-soluble acrylic monomer component exhibit transparency even when mixed with 18% by mass or more of water at 23 ° C.
- 水溶性アクリル系モノマーが、水酸基含有アクリル系モノマーである請求項３記載の吸水性シート。 The water-absorbent sheet according to claim 3, wherein the water-soluble acrylic monomer is a hydroxyl group-containing acrylic monomer.
- 水酸基含有アクリル系モノマーが、４－ヒドロキシブチルアクリレート、２－ヒドロキシプロピルアクリレート、又は２－ヒドロキシエチルメタクリレートである請求項４記載の吸水性シート。 5. The water absorbent sheet according to claim 4, wherein the hydroxyl group-containing acrylic monomer is 4-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, or 2-hydroxyethyl methacrylate.
- 含水アクリル系モノマー膜が、光重合開始剤と架橋剤とを含有する請求項１～５のいずれかに記載の吸水性シート。 The water-absorbent sheet according to any one of claims 1 to 5, wherein the water-containing acrylic monomer film contains a photopolymerization initiator and a crosslinking agent.
- 含水アクリル系モノマー膜が、水溶性アクリル系モノマー成分１００質量部に対し、光重合開始剤を０．０１～１質量部、架橋剤を０．０１～５質量部の割合で含有する請求項６記載の吸水性シート。 The water-containing acrylic monomer film contains 0.01 to 1 part by weight of a photopolymerization initiator and 0.01 to 5 parts by weight of a crosslinking agent with respect to 100 parts by weight of a water-soluble acrylic monomer component. The water-absorbent sheet as described.
- 含水光硬化膜の含水量が、５～５０質量％である請求項１～７のいずれかに記載の吸水性シート。 The water-absorbent sheet according to any one of claims 1 to 7, wherein the water-containing photocured film has a water content of 5 to 50% by mass.
- 含水光硬化膜のヘイズ度が、８％以下である請求項１～８のいずれかに記載の吸水性シート。 The water-absorbent sheet according to any one of claims 1 to 8, wherein the water-containing photocured film has a haze degree of 8% or less.
- 含水光硬化膜の吸水性が、自重に対し１０質量％以上である請求項１～９のいずれかに記載の吸水性シート。 10. The water absorbent sheet according to claim 1, wherein the water-containing photocured film has a water absorption of 10% by mass or more based on its own weight.
- 水溶性アクリル系モノマー成分と水とを含有する含水アクリル系モノマー膜の含水光硬化膜を有する吸水性シートの製造方法であって：
２３℃で１８質量％以上の水と混和したときに透明性を示す水溶性アクリル系モノマー成分と、光重合開始剤と、架橋剤と、水とを含有する含水光硬化性アクリル系モノマー組成物をベースフィルムに成膜することにより含水アクリル系モノマー膜を形成する工程；
含水アクリル系モノマー膜に透明剥離フィルムを積層する工程；及び
含水アクリル系モノマー膜に対し、透明剥離フィルム若しくはベースフィルム側から紫外線を照射することにより、含水アクリル系モノマー膜の含水量を保持したまま含水光硬化膜を形成する工程；
を有する製造方法。 A method for producing a water-absorbent sheet having a water-containing photocured film of a water-containing acrylic monomer film containing a water-soluble acrylic monomer component and water:
A water-containing photocurable acrylic monomer composition comprising a water-soluble acrylic monomer component that exhibits transparency when mixed with 18% by mass or more of water at 23 ° C., a photopolymerization initiator, a crosslinking agent, and water. Forming a water-containing acrylic monomer film by forming a film on the base film;
A step of laminating a transparent release film on the water-containing acrylic monomer film; and irradiating the water-containing acrylic monomer film with ultraviolet rays from the transparent release film or the base film side, while maintaining the water content of the water-containing acrylic monomer film Forming a hydrous photocured film;
A manufacturing method comprising: - ２３℃で１８質量％以上の水と混和したときの水溶性アクリル系モノマー成分の透明性が、へイズ度８％以下である請求項１１記載の製造方法。 The method according to claim 11, wherein the transparency of the water-soluble acrylic monomer component when mixed with 18% by mass or more of water at 23 ° C. has a haze degree of 8% or less.
- 水溶性アクリル系モノマー成分を構成するすべての水溶性アクリル系モノマーとして、２３℃で１８質量％以上の水と混和しても透明性を示すものを使用する請求項１１又は１２記載の製造方法。 The production method according to claim 11 or 12, wherein all water-soluble acrylic monomers constituting the water-soluble acrylic monomer component are transparent even when mixed with water of 18% by mass or more at 23 ° C.
- 水溶性アクリル系モノマーとして、水酸基含有アクリル系モノマーを使用する請求項１３記載の製造方法。 The production method according to claim 13, wherein a hydroxyl group-containing acrylic monomer is used as the water-soluble acrylic monomer.
- 水酸基含有アクリル系モノマーとして、４－ヒドロキシブチルアクリレート、２－ヒドロキシプロピルアクリレート、又は２－ヒドロキシエチルメタクリレートを使用する請求項１４記載の製造方法。 The production method according to claim 14, wherein 4-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, or 2-hydroxyethyl methacrylate is used as the hydroxyl-containing acrylic monomer.
- 含水アクリル系モノマー膜中の含水量が、５～５０質量％である請求項１１～１５のいずれかに記載の製造方法。 The production method according to any one of claims 11 to 15, wherein the water content in the water-containing acrylic monomer film is 5 to 50% by mass.
- 含水アクリル系モノマー膜が、光重合開始剤と架橋剤とを含有する請求項１１～１６のいずれかに記載の製造方法。 The production method according to any one of claims 11 to 16, wherein the water-containing acrylic monomer film contains a photopolymerization initiator and a crosslinking agent.
- 含水アクリル系モノマー膜が、水溶性アクリル系モノマー成分１００質量部に対し、光重合開始剤を０．０１～１質量部、架橋剤を０．０１～５質量部の割合で含有する請求項１７記載の製造方法。 The water-containing acrylic monomer film contains 0.01 to 1 part by weight of a photopolymerization initiator and 0.01 to 5 parts by weight of a crosslinking agent with respect to 100 parts by weight of a water-soluble acrylic monomer component. The manufacturing method as described.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016159516A JP6828301B2 (en) | 2016-08-16 | 2016-08-16 | Water-absorbent sheet |
| JP2016-159516 | 2016-08-16 |
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| Publication Number | Publication Date |
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| WO2018034116A1 true WO2018034116A1 (en) | 2018-02-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2017/026984 WO2018034116A1 (en) | 2016-08-16 | 2017-07-26 | Water-absorbing sheet |
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| Country | Link |
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| JP (1) | JP6828301B2 (en) |
| TW (1) | TW201818979A (en) |
| WO (1) | WO2018034116A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07265605A (en) * | 1994-02-10 | 1995-10-17 | Nippon Shokubai Co Ltd | Method for removing water in oil |
| JP2011132279A (en) * | 2009-12-22 | 2011-07-07 | Nitto Denko Corp | Method for producing polymer member containing hydrous substance |
| JP2012066407A (en) * | 2010-09-21 | 2012-04-05 | Nitto Denko Corp | Method for manufacturing polymer member, and polymer member |
| JP2013063605A (en) * | 2011-09-20 | 2013-04-11 | Nitto Denko Corp | Method for manufacturing polymer member, and polymer member |
| WO2016059973A1 (en) * | 2014-10-15 | 2016-04-21 | デクセリアルズ株式会社 | Method for producing water-absorbent polymer sheet |
-
2016
- 2016-08-16 JP JP2016159516A patent/JP6828301B2/en active Active
-
2017
- 2017-07-26 WO PCT/JP2017/026984 patent/WO2018034116A1/en active Application Filing
- 2017-08-07 TW TW106126562A patent/TW201818979A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07265605A (en) * | 1994-02-10 | 1995-10-17 | Nippon Shokubai Co Ltd | Method for removing water in oil |
| JP2011132279A (en) * | 2009-12-22 | 2011-07-07 | Nitto Denko Corp | Method for producing polymer member containing hydrous substance |
| JP2012066407A (en) * | 2010-09-21 | 2012-04-05 | Nitto Denko Corp | Method for manufacturing polymer member, and polymer member |
| JP2013063605A (en) * | 2011-09-20 | 2013-04-11 | Nitto Denko Corp | Method for manufacturing polymer member, and polymer member |
| WO2016059973A1 (en) * | 2014-10-15 | 2016-04-21 | デクセリアルズ株式会社 | Method for producing water-absorbent polymer sheet |
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| Publication number | Publication date |
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| TW201818979A (en) | 2018-06-01 |
| JP6828301B2 (en) | 2021-02-10 |
| JP2018027998A (en) | 2018-02-22 |
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