WO2019013207A1

WO2019013207A1 - Nonfreezing composition and nonfreezing polymer

Info

Publication number: WO2019013207A1
Application number: PCT/JP2018/026038
Authority: WO
Inventors: 正和金子
Original assignee: イムラ・ジャパン株式会社
Priority date: 2017-07-12
Filing date: 2018-07-10
Publication date: 2019-01-17
Also published as: JP2019019167A

Abstract

A nonfreezing composition containing a crosslinking monomer represented by general formula (1): [in formula (1), R1 represents a hydrogen atom or methyl group and R2 represents a group represented by general formula (2): [in formula (2), R3 represents a hydrogen atom or methyl group] or a group represented by general formula (3): [in formula (3), R4 represents an alkylene group having 1-4 carbons and R5 represents a hydrogen atom or methyl group]] and a radical polymerizable monomer that is an ester compound other than the crosslinking monomer and that has a functional group capable of undergoing radical polymerization with the crosslinking monomer, wherein the proportion of the crosslinking monomer to the total moles of the crosslinking monomer and radical polymerizable monomer is 2.5-70 mol%.

Description

Non-icing composition and non-icing polymer

The present invention relates to non-icing compositions and non-icing polymers.

Conventionally, various damage has occurred due to icing or snowing on the surface of the structure. For example, icing or icing on the surface of ships, aircraft, vehicles, roads, railways, road signs, traffic lights, etc. is a serious safety issue, and in wind power generation facilities etc, the amount of power generation decreases due to winter icing. is happening. In addition, if icing occurs on the surface of a power transmission grid, a transceiver, etc. and ice is accumulated, there is a possibility that an accident or a failure may be caused by the load. As a method of preventing such icing and snow deposition, for example, a method of removing ice and snow adhering to and accumulated on the surface of a structure using a heater or a deicing solution is known. However, such a method requires power and an anti-icing solution, and thus has the problem of being time-consuming and costly.

Further, as another method of preventing icing and snow deposition, for example, a method of applying a paint having anti-icing and anti-snow properties to a surface of a structure where icing is expected is also known. Examples of the paint include modified resins of silicone resins and fluorocarbon resins. For example, in JP-A-10-120941 (Patent Document 1), polyfluoroalkyl group-containing vinyl monomers and silicone-based vinyl monomers JP-A-58-65779 (Patent Document 2) describes a water-repellent coating composition obtained by mixing a specific amount of a powder having an average particle diameter of 0.1 to 50 μm with a copolymer thereof. Compositions for anti-icing materials are described which consist of specific organopolysiloxane resins and alkali metal compounds. Further, in JP-A-2017-2269 (Patent Document 3), as a paint for a large-sized structure such as an aircraft, a mixture of a room temperature reaction curing resin and a particulate fluorine resin at a specific ratio is used. Mixed paints are described.

Furthermore, JP-A-5-230161 (patent document 4) mainly describes a graft copolymer comprising a main polymer comprising a vinyl polymer and a branched polymer comprising an organopolysiloxane and a branched polymer comprising polyoxyalkylene. JP-A-5-105723 (Patent Document 5) describes a water / oil repellent resin comprising a polymer containing a specific fumaric acid diester as a constituent unit. It is done.

However, all of these conventional anti-icing and anti-snow protection paints and polymers result in a reduction in the contact area between the surface of the structure and water droplets, that is, by imparting water repellency to the surface of the structure. In the interface where the surface of the structure and the ice are in contact with each other, the adhesion of the ice to the surface is not sufficient as the non-icing property which is suppressed. In addition, it has been still difficult to stably achieve the anti-icing effect.

Unexamined-Japanese-Patent No. 10-120941 gazette Japanese Patent Application Laid-Open No. 58-65779 JP 2017-2269 A JP-A-5-230161 JP-A-5-105723

The present invention has been made in view of the problems of the above prior art, and provides a non-icing polymer having excellent non-icing properties, and a non-icing composition capable of obtaining the same. The purpose is to

As a result of intensive studies to achieve the above object, the present inventor has found that a specific crosslinkable monomer having two vinyl groups, and a radically polymerizable monomer having a functional group capable of radically polymerizing with the crosslinkable monomer. It has been found that in the copolymer obtained by radical copolymerization of at a specific ratio, the adhesion of ice to the surface of the copolymer is extremely small, and remarkable non-icing property is exhibited. Also, the extremely low adhesion described above is achieved even if the water repellency of the surface of the copolymer is low, and such non-icing property is adhesion of ice within the interface where the surface of the copolymer is in contact with ice. Were found to be exhibited and suppressed, so that in the copolymer, icing was stably suppressed. Furthermore, since the light transmittance of the above-mentioned copolymer is sufficiently high, the present inventor applies it to a window glass or the like, or uses it as a substitute material for a material such as a structure or glass which requires transparency. It has been found that it is possible to complete the present invention.

That is, the non-icing composition of the present invention has the following general formula (1):

[In Formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a group represented by the following general formula (2):

[In the formula (2), ^{R 3} represents a hydrogen atom or a methyl group. ]
Or a group represented by the following general formula (3):

[In the formula (3), R ⁴ represents an alkylene group having 1 to 4 carbon atoms, and R ⁵ represents a hydrogen atom or a methyl group. ]
Represents a group represented by ]
And an ester compound other than the crosslinkable monomer, wherein the crosslinkable monomer is a radically polymerizable monomer having a functional group capable of radically polymerizing with the crosslinkable monomer, and
The ratio of the crosslinking monomer to the total mole of the crosslinking monomer and the radically polymerizable monomer is 2.5 to 70 mol%.
It is a composition.

In the non-icing composition of the present invention, the radically polymerizable monomer has the following general formula (4):

[In the formula (4), R ⁶ represents an alkyl group having 1 to 8 carbon atoms which may be substituted by a fluorine atom, and R ⁷ represents a hydrogen atom or a methyl group. ]
It is preferable that it is at least one selected from the group consisting of a compound represented by: and diallyl terephthalate.

The non-icing polymer of the present invention is a copolymer obtained by polymerizing the crosslinkable monomer and the polymerizable monomer in the non-icing composition of the present invention.

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the non-icing polymer which has the outstanding non-icing property, and the non-icing composition which can obtain it.

FIG. 10 is a graph showing the relationship between the vinyl methacrylate content and the non-icing recovery rate in the substrates obtained in Examples 3 and 7 to 9 and Comparative Examples 4 and 8 to 9. FIG. FIG. 16 is a graph showing the relationship between the vinyl methacrylate content and the non-icing recovery rate in the substrates obtained in Examples 5, 10 to 14 and Comparative Examples 6 and 10 to 11. FIG. 16 is a graph showing the relationship between the divinyl adipate content and the non-icing recovery rate in the substrates obtained in Examples 6, 15 to 17 and Comparative Examples 2 and 12 to 13. FIG.

Hereinafter, the present invention will be described in detail in line with its preferred embodiments.

First, the non-icing composition of the present invention will be described. The non-icing composition of the present invention has the following general formula (1):

[In the formula (3), R ⁴ represents an alkylene group having 1 to 4 carbon atoms, and R ⁵ represents a hydrogen atom or a methyl group. ]
Represents a group represented by ]
And an ester compound other than the crosslinkable monomer, wherein the crosslinkable monomer is a radically polymerizable monomer having a functional group capable of radically polymerizing with the crosslinkable monomer, and
A ratio of the crosslinkable monomer is 2.5 to 70% by mole based on a total mole of the crosslinkable monomer and the radically polymerizable monomer;
It is characterized by

The crosslinkable monomer according to the present invention has the following general formula (1):

It is a compound represented by

In the formula (1), R ¹ represents a hydrogen atom or a methyl group. Among them, R ¹ is a hydrogen from the viewpoint that the degree of electron donating is lower, so the electron density on the unsaturated bond is smaller and the crosslinkable monomer tends to be relatively easily radically polymerized. Atoms are preferred.

Further, in the above formula (1), R ² is a compound represented by the following general formula (2):

Or a group represented by the following general formula (3):

Represents a group represented by

In the above formula (2), R ³ represents a hydrogen atom or a methyl group. Among these, as R ³ , a methyl group is preferable from the viewpoint that the crystal strength of the obtained polymer tends to be higher and the viewpoint that it is relatively easy to obtain as a methacrylic compound in the market.

Further, in the above formula (3), R ⁴ represents an alkylene group having 1 to 4 carbon atoms. The number of carbon atoms is preferably 1 to 2 from the viewpoint that the crystal strength of the resulting polymer tends to decrease when the number of carbon atoms is too large. Further, in the formula (3), R ⁵ is a hydrogen atom or a methyl group. Among them, R ⁵ is a hydrogen from the viewpoint that the electron density on the unsaturated bond is lower and the crosslinkable monomer tends to be relatively easy to radically polymerize because the degree of electron donating is lower. Atoms are preferred.

As the crosslinkable monomer, one type may be used alone, or two or more types may be used in combination.

Examples of such crosslinkable monomers include vinyl methacrylate, divinyl adipate, divinyl malonate, divinyl glutarate and divinyl succinate, and two or more of them may be used alone. You may use in combination. Among them, the crosslinkable monomer according to the present invention is at least one selected from the group consisting of vinyl methacrylate and divinyl adipate from the viewpoint of tending to be more readily available in the market and relatively inexpensive. Is more preferred.

The crosslinkable monomer according to the present invention has two vinyl groups (CH ₂ CRCR— [R: R ¹ , R ³ , R ⁵ ]), and thus reacts with a radical polymerizable monomer described later to crosslink these. To obtain the non-icing polymer of the present invention. In addition, the crosslinkable monomer which is also an ester compound (in the present invention, a compound having an ester bond structure (-COO-) in the molecule as the "ester compound" in the present invention) has an ester bond structure in the polymer obtained The inventors infer that the non-icing polymer of the present invention can exhibit remarkable non-icing properties by having a fixed amount of such an ester bond structure.

The radically polymerizable monomer according to the present invention is an ester compound having an ester bond structure (-COO-) in the molecule other than the crosslinkable monomer. The inventors of the present invention have found that the non-icing polymer of the present invention can exhibit remarkable non-icing properties by introducing an ester bond structure into a polymer obtained also by such a radically polymerizable monomer. The inventor guesses.

The radically polymerizable monomer according to the present invention also has a functional group capable of radically polymerizing with the crosslinkable monomer. The crosslinkable monomer and the radically polymerizable functional group are a functional group capable of radically polymerizing the vinyl group of the crosslinkable monomer, and examples thereof include a vinyl group, an acryl group, a methacryl group, a styryl group, an allyl group and a vinyloxy group. Can be mentioned. The radically polymerizable monomer according to the present invention may have two or more of the above functional groups, and in that case, two or more of them may be used alone as a plurality of functional groups. May be used in combination. As such functional groups, from the viewpoint that the content of the ester bond structure in the resulting polymer tends to be higher and more excellent non-icing property is exhibited, unsaturated including the ester bond structure It is preferably a functional group, more preferably at least one selected from the group consisting of an acrylic group and a methacrylic group, and more preferably one or two in one molecule.

As a compound preferable as a radically polymerizable monomer concerning this invention, following General formula (4):

The compound represented by these is mentioned.

In the above formula (4), R ⁶ represents an alkyl group having 1 to 8 carbon atoms which may be substituted by a fluorine atom. The number of carbon atoms is preferably 1 to 5, and more preferably 1 to 2, from the viewpoint that the crystal strength of the resulting polymer tends to decrease when the side chain is too long. As such an alkyl group which may be substituted by a fluorine atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, benzyl group and structural isomers thereof are mentioned. These may be used alone or in combination of two or more. Among them, R ⁶ is selected from the group consisting of a methyl group, an ethyl group and structural isomers thereof, from the viewpoint that the crystal strength of the resulting polymer tends to decrease when the side chain is too long. More preferably, it is at least one of

Further, in the above formula (4), R ⁷ represents a hydrogen atom or a methyl group. Among these, as R ⁷ , a methyl group is preferable from the viewpoint that the crystal strength of the resulting polymer tends to be higher and the viewpoint that it is relatively easy to obtain as a methacrylic compound in the market.

Examples of such radically polymerizable monomers represented by the formula (4) include methyl methacrylate, hexyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and 1,1,1,3, methacrylates. 3,3-Hexafluoropropyl, trifluoromethyl methacrylate, methyl acrylate, hexyl acrylate, 2,2,2-trifluoroethyl acrylate, 1,1,1,3,3,3-hexafluoro acrylate Propyl may be mentioned, and one of these may be used alone, or two or more may be used in combination. Among these, from the viewpoint that the crystal strength of the resulting polymer tends to decrease when the side chain substituent is too long, and from the viewpoint that the cold resistance tends to be further improved by being substituted with a fluorine atom. Is more preferably at least one selected from the group consisting of trifluoromethyl methacrylate and 2,2,2-trifluoroethyl methacrylate.

Moreover, as another compound preferable as a radically polymerizable monomer concerning this invention, a diallyl terephthalate is also mentioned, for example.

As a radically polymerizable monomer which concerns on this invention, you may use individually by 1 type, or may be used in combination of 2 or more type.

In the non-icing composition of the present invention, the ratio of the crosslinkable monomer to the total mole of the crosslinkable monomer and the radical polymerizable monomer ({mole number of crosslinkable monomer / (mole number of crosslinkable monomer + Number of moles of radically polymerizable monomer)} × 100; when each monomer is a mixture of 2 or more types, it is necessary that the total number of moles (hereinafter the same) is 2.5 to 70 mole%. is there. When the proportion of the crosslinkable monomer is in the above range, remarkable non-icing property is exhibited in the non-icing polymer of the present invention which is a copolymer obtained by polymerizing these monomers.

The ratio of the crosslinkable monomer to the total mole of the crosslinkable monomer and the radical polymerizable monomer is 2.5 to 65% by mole from the viewpoint of exhibiting a particularly excellent non-icing property. And preferably 5 to 30 mol%.

The non-icing composition of the present invention may further contain other components other than the crosslinkable monomer and the radical polymerizable monomer, as long as the effects of the present invention are not impaired. Examples of the other components include a polymerization initiator, a solvent, an organic pigment, an inorganic pigment, a metal catalyst used in a polymerization reaction, etc. Even if one of these is used alone, it is used in combination of two or more. You may use it.

Examples of the polymerization initiator include radical polymerization initiators, and more specifically, organic peroxides such as benzoyl peroxide (BPO), hydroperoxide, t-butylperoxy-2-ethylhexanoate and the like Dihalogen such as chlorine; 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobisisovaleronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2, Azo compounds such as 2′-azobis (2-methylbutyronitrile) may be mentioned, and one of these may be used alone, or two or more may be used in combination. Among them, the polymerization initiator is more preferably at least one selected from the group consisting of thermally decomposable initiators such as benzoyl peroxide and 2,2-azobisisobutyronitrile.

The solvent is preferably an aprotic solvent which does not inhibit the radical polymerization reaction, and examples thereof include hexane, dichloromethane, carbon tetrachloride, THF, benzene, diethyl ether, DMSO, DMF and the like. One type may be used alone or two or more types may be used in combination.

When the non-icing composition of the present invention further contains these other components, the content (total content in the case of a mixture of two or more kinds) of the same non-icing composition The content is preferably 5% by mass or less based on the total mass, and more preferably 0.1 to 1% by mass.

Next, the non-icing polymer of the present invention will be described. The non-icing polymer of the present invention is characterized in that it is a copolymer obtained by polymerizing the crosslinkable monomer and the radical polymerizable monomer in the non-icing composition.

As the polymerization method, conventionally known methods can be suitably adopted as radical polymerization methods such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, etc. For example, the crosslinkable monomer, the radical polymerizable monomer, and The non-icing composition containing the thermally decomposable initiator as the polymerization initiator is treated for 0.1 to 2 hours at a temperature (preferably 100 to 150 ° C.) above the decomposition point of the thermally decomposable polymerization initiator The method of heating is mentioned. The heating time and temperature can be appropriately adjusted according to the composition of the non-icing composition.

The non-icing polymer of the present invention is a copolymer obtained by polymerizing the cross-linking monomer and the radical polymerizable monomer in the non-icing composition, and thus is derived from the cross-linking monomer It is a network-like polymer including a structural unit and a structural unit derived from the radical polymerizable monomer, and has an ester bond structure (—COO—) in the molecule. The structural unit derived from the crosslinkable monomer and the structural unit derived from the radical polymerizable monomer may have any form of random and block, or a mixture of these. Further, the non-icing polymer may be saturated or unsaturated.

As such non-icing polymers, for example, the following general formula (11):

[In the formula (11), a ₁₁ , b ₁₁ and c ₁₁ each independently represent an integer of 1 or more representing the number of repetitions of each unit enclosed by key brackets ([] (same below), * (Asterisk (the same shall apply hereinafter)) indicates a binding site to another repeating unit. ]
The compound containing the repeating unit represented by these is mentioned. Here, in the formula (11), each unit having a repeating number of a ₁₁ and b ₁₁ represents a structural unit derived from the crosslinkable monomer, and a unit having a repeating number of c ₁₁ is a radically polymerizable monomer. The structural unit derived from is shown. Each of these units may be in any form of random and block, and may not be combined in the order shown in Formula (11), or may be combined in random order.

As the non-icing polymer of the present invention, for example, the following general formula (12):

[In the formula (12), a ₁₂ , b ₁₂ and c ₁₂ each independently represent an integer of 1 or more representing the number of repetitions of each unit enclosed in a key bracket, and * represents one or more other repeating units The binding site is shown. ]
A compound containing a repeating unit represented by the following general formula (13):

[In the formula (13), a ₁₃ , b ₁₃ and c ₁₃ each independently represent an integer of 1 or more representing the number of repetitions of each unit enclosed by a key bracket, and * represents one or more other repeating units The binding site is shown. ]
A compound containing a repeating unit represented by the following general formula (14):

[In the formula (14), a ₁₄ , b ₁₄ , c ₁₄ and d ₁₄ each independently represent an integer of 1 or more representing the number of repetitions of each unit enclosed in a key bracket, and * represents another repetition The binding site to the unit is shown. ]
A compound containing a repeating unit represented by the following general formula (15):

[In the formula (15), a ₁₅ , b ₁₅ and c ₁₅ each independently represent an integer of 1 or more representing the number of repetitions of each unit enclosed in a key bracket, and * represents one or more other repeating units The binding site is shown. ]
A compound containing a repeating unit represented by the following general formula (16):

[In the formula (16), a ₁₆ , b ₁₆ and c ₁₆ each independently represent an integer of 1 or more representing the number of repetitions of each unit enclosed by a key bracket, and * represents one or more other repeating units The binding site is shown. ]
The compound containing the repeating unit represented by these is mentioned. In the formulas (12) to (16), each unit may independently be in any form of random or block, and may not be combined in the order shown in each formula, and random order It may be bonded by

In the non-icing polymer of the present invention, the ratio of the constituent unit derived from the crosslinkable monomer to the total mole of the constituent unit derived from the crosslinkable monomer and the constituent unit derived from the radical polymerizable monomer is 2 5 to 70 mol% (more preferably 2.5 to 60 mol%, 5 to 30 mol%). When the ratio of the constituent unit derived from the crosslinkable monomer is in the above range, remarkable non-icing property tends to be exhibited.

In the non-icing polymer of the present invention, each monomer in the non-icing polymer has a tendency to exhibit particularly excellent non-icing property as the content of the ester bond structure. It is preferable that it is 2.5-100 mol% in the ratio of the structural unit containing the ester bond structure in the whole structural unit derived from, it is more preferable that it is 70-100 mol%, and it is 99-100 mol%. Is more preferred.

As the non-icing polymer of the present invention, components other than the constituent unit derived from the crosslinkable monomer and the constituent unit derived from the radical polymerizable monomer can be further added within a range not inhibiting the effect of the present invention. You may contain. Examples of the other components include unreacted raw materials, unreacted polymerization initiators, residual solvents, organic pigments, inorganic pigments, metal catalysts used for the polymerization reaction, etc. One of these may be used alone. Alternatively, two or more may be used in combination.
When the non-icing polymer of the present invention further contains these other components, the content (total content in the case of a mixture of two or more) of the same non-icing polymer It is preferable that it is 5 mass% or less with respect to the total mass.

The non-icing polymer of the present invention can be formed into any form according to the application and the type of the object to be treated. The shape, size, thickness and the like of the molded body are not particularly limited, and the use thereof is not particularly limited. For example, by applying the non-icing composition as a coating agent to the surface of an object to be treated, and polymerizing the crosslinkable monomer and the radically polymerizable monomer, the non-icing compound on the surface of the object is treated It is possible to form a coating film containing an object. The object to be treated is not particularly limited, and examples thereof include structures in which icing such as ships, aircraft, vehicles, roads, railways, road signs, traffic lights, and the like are expected. Moreover, it does not restrict | limit especially as a material of the said structure, For example, glass, fiber, paper, wood, leather, fur, a brick, cement, a metal, a metal oxide, porcelain, and plastics are mentioned. Furthermore, the method of application is not particularly limited, and a conventionally known method can be adopted, and examples thereof include a method of applying by spray application or brushing.

Furthermore, by using the non-icing polymer of the present invention as it is as a solid, powder or the like, it can be used as the material of the above-mentioned structure in which icing is expected. In addition, the non-icing polymer of the present invention has a sufficiently high light transmittance (preferably, when the content of the other components is 1% by mass or less, the thickness of the non-icing polymer) Light transmittance of 94% or more when light is vertically incident on a substrate surface of 1.8 mm), and therefore, a molded article having an arbitrary form is required to be transparent as it is, such as a structure or glass depending on the application. Can be used as a substitute material for

Hereinafter, the present invention will be more specifically described based on examples and comparative examples, but the present invention is not limited to the following examples. In addition, the icing force measurement and the ice drop measurement in the board | substrate obtained by each Example and the comparative example were performed by the following methods, respectively.

<Icing force measurement>
First, a stainless steel ring for ice formation (height: 15 mm, diameter (inner diameter): 25.4 mm) is placed on the substrate surface, cooled at -10 ° C for 1 hour, and then distilled water at 4 ° C is contained in the stainless ring. I poured it. The mixture was allowed to stand for an additional hour to freeze the distilled water and to freeze ice on the substrate surface. Next, load is applied from the side of the stainless steel ring in the direction parallel to the substrate surface under the condition of temperature: -10 ° C using the icing force measuring device of the Hokkaido Comprehensive Research Organization industrial testing station, The load when the interface with ice was peeled off was measured, and the load per area of the interface (area in the stainless steel ring) was taken as the icing force (kgf / cm ² ). At this time, those for which the load was not measured, that is, those for which the load was less than the measurement limit of the icing force measurement apparatus, were regarded as “ND”. The measurement limit of the icing force measuring device was 0.06 kgf / cm ² .

<Ice drop measurement>
First, each substrate was cooled at −10 ° C. for 1 hour, and then 100 μL of distilled water at 4 ° C. was dropped on the substrate surface. The mixture was allowed to stand for an additional hour to freeze the distilled water and to freeze ice on the substrate surface. Next, while maintaining the temperature at -10 ° C, the substrate is rotated by 180 ° C so that the ice-frozen surface is the lower surface, and the ice falling by itself or by glide is determined as "ice falling". did. The test was performed ten times, and the ratio of the number of times it was determined that the ice was dropped ((number of ice drops / 10) × 100) was taken as the non-icing recovery rate (%).

Example 1
The compound containing the repeating unit represented by the said General formula (11) was obtained. That is, first, 0.56 g (0.005 mol) of vinyl methacrylate as the A component and 2.44 g of methyl methacrylate as the B component in a cylindrical glass container at room temperature (about 25 ° C. (same below)) 0.024 mol) were mixed until homogeneous. Next, 75 mg of a thermally decomposable polymerization initiator (50% benzoyl peroxide paste (manufactured by Nisshin EM Co., Ltd.)) in terms of benzoyl peroxide was added to obtain a reaction composition. Next, the glass container was placed on a hot plate heated to 120 ° C., and the reaction composition was stirred for 10 to 20 minutes to dissolve insolubles, and all of the A and B components were polymerized. When the reaction is completed and white smoke is produced, the temperature of the reaction composition is lowered to room temperature with cold water, and a substrate-like formed body (height: 3.65 mm, diameter: containing the title compound (copolymer) 26.7 mm). The obtained substrate spontaneously released from the surface of the glass container. The amounts (mol) of the components A and B in the obtained substrate are shown in Table 1 below. Moreover, the content rate of the vinyl methacrylate (A) with respect to the total mole of the component A and the component B in the preparation amount (in the reaction composition) ({A / (A + B)} × 100, in the table: “A / (A + B) Table 1 also shows) [mol%] ", and so forth.

(Example 2)
The compound containing the repeating unit represented by the said General formula (12) was obtained. That is, in the same manner as in Example 1 except that 1.21 g (0.011 mol) of vinyl methacrylate as the A component and 2.29 g (0.013 mol) of hexyl methacrylate as the B component were used A substrate-like molded product containing the polymer) was obtained. The amounts of the components A and B and the content of the vinyl methacrylate (A) in the obtained substrate are shown in Table 1.

(Example 3)
The compound containing the repeating unit represented by the said General formula (13) was obtained. That is, Example 1 except that 0.19 g (0.002 mol) of vinyl methacrylate as the A component and 2.36 g (0.014 mol) of 2,2,2-trifluoroethyl methacrylate as the B component were used. A substrate-like molded product containing the title compound (copolymer) was obtained in the same manner as in the above. The amounts of the components A and B and the content of the vinyl methacrylate (A) in the obtained substrate are shown in Table 1.
(Example 4)
The compound containing the repeating unit represented by the said General formula (14) was obtained. That is, 1.21 g (0.011 mol) of vinyl methacrylate as the component A, 0.88 g (0.005 mol) of hexyl methacrylate as the component B, and 1.89 g of 2,2,2-trifluoroethyl methacrylate A substrate-like molded product containing the title compound (copolymer) was obtained in the same manner as in Example 1 except that 0. 11 mol) was used. The amounts of the components A and B and the content of the vinyl methacrylate (A) in the obtained substrate are shown in Table 1.
(Example 5)
The compound containing the repeating unit represented by the said General formula (15) was obtained. That is, first, 0.93 g (0.008 mol) of vinyl methacrylate as component A and 2.24 g (0.009 mol) of diallyl terephthalate as component B become uniform in a cylindrical glass container at room temperature. Mixed up. Next, 75 mg of a thermally decomposable polymerization initiator (50% benzoyl peroxide paste (manufactured by Nisshin EM Co., Ltd.)) in terms of benzoyl peroxide was added to obtain a reaction composition. Then, the glass container was placed on a hot plate heated to 120 ° C., and the reaction composition was stirred for 10 to 20 minutes to dissolve insolubles. Then, the temperature is brought to 170 ° C., and components A and B are all polymerized for 5 hours, and a substrate-like molded product (height: 3.65 mm, diameter: 26.7 mm) containing the title compound (copolymer) I got The obtained substrate spontaneously released from the surface of the glass container. The amounts of the components A and B and the content of the vinyl methacrylate (A) in the obtained substrate are shown in Table 1.
(Example 6)
The compound containing the repeating unit represented by the said General formula (16) was obtained. That is, in the same manner as in Example 5 except that 0.24 g (0.0012 mol) of divinyl adipate was used as the A component, and 1.12 g (0.005 mol) of diallyl terephthalate was used as the B component. A substrate-like molded product containing the polymer) was obtained. The amounts of the components A and B and the content of divinyl adipate (A) in the obtained substrate are shown in Table 1.

(Comparative example 1)
The following general formula (21):

[In the formula (21), a ₂₁ and b ₂₁ each independently represent an integer of 1 or more representing the number of repetitions of each unit enclosed in a bracket, and * represents a binding site to another repeating unit] Each unit may be in any form of random and block. ]
The compound containing the repeating unit represented by was obtained. That is, a substrate-like molded product containing the title compound (homopolymer) in the same manner as in Example 1 except that 3.63 g (0.032 mol) of vinyl methacrylate was used as the component A without using the component B. I got The amount and content of the component A in the obtained substrate are shown in Table 1.

(Comparative example 2)
The following general formula (22):

[In the formula (22), a ₂₂ and b ₂₂ each independently represent an integer of 1 or more representing the number of repetitions of each unit enclosed in brackets, and * represents a binding site to another repeating unit Each unit may be in any form of random and block. ]
The compound containing the repeating unit represented by was obtained. That is, a substrate-like molded product containing the title compound (homopolymer) in the same manner as in Example 1 except that component B was not used and 1.18 g (0.006 mol) of divinyl adipate was used as component A. I got The amount and content of the component A in the obtained substrate are shown in Table 1.

(Comparative example 3)
The following general formula (23):

[In formula (23), a ₂₃ and b ₂₃ each independently represent an integer of 1 or more representing the number of repetitions of each unit enclosed in brackets, and * represents a binding site to another repeating unit Each unit may be in any form of random and block. ]
The compound containing the repeating unit represented by was obtained. That is, a substrate-like molded product containing the title compound (homopolymer) was obtained in the same manner as in Example 1 except that component B was not used and 2.69 g (0.032 mol) of hexadiene was used as component A. The The amount and content of the component A in the obtained substrate are shown in Table 1.

(Comparative example 4)
The following general formula (24):

Wherein (24), a ₂₄ is 1 or more integer indicating the number of repetitions of units enclosed in brackets, * indicates the binding site of other repeating units. ]
The compound containing the repeating unit represented by was obtained. That is, the title compound (homopolymer) was prepared in the same manner as in Example 1 except that 2.36 g (0.014 mol) of 2,2,2-trifluoroethyl methacrylate was used as the component B without using the component A. ) Was obtained. The amount of B component and the content of A component in the obtained substrate are shown in Table 1.

(Comparative example 5)
The following general formula (25):

[In the formula (25), a ₂₅ and b ₂₅ each independently represent an integer of 1 or more representing the number of repetitions of each unit enclosed in brackets, and * represents a binding site to another repeating unit Each unit may be in any form of random and block. ]
The compound containing the repeating unit represented by was obtained. That is, without using the component A, 2.36 g (0.014 mol) of 2,2,2-trifluoroethyl methacrylate as the component B and 1H, 1H, 2H, 2H, 2H-tridecafluoro-n-octyl methacrylate 3 A substrate-like molded product containing the title compound (copolymer) was obtained in the same manner as in Example 1 except that .02 g (0.007 mol) was used. The amount of B component and the content of A component in the obtained substrate are shown in Table 1.

(Comparative example 6)
The following general formula (26):

[Wherein, in the formula (26), a ₂₆ is an integer of 1 or more that indicates the number of repetitions of the unit enclosed by brackets, and * indicates a binding site to another repeating unit. ]
The compound containing the repeating unit represented by was obtained. That is, a substrate-like molded article containing the title compound (homopolymer) in the same manner as in Example 5 except that component A was not used and 3.36 g (0.014 mol) of diallyl terephthalate was used as component B. I got The amount of B component and the content of A component in the obtained substrate are shown in Table 1.

(Comparative example 7)
First, an anti-icing spray (silicone polymer, "UNIX (Unix) Meltec Spray") is described on the side of a 2 mm-thick PET plate (manufactured by Acrisunday Co., Ltd.) cut into 5 cm square, in the manual of the same spray. Spray applied according to the method of This was sufficiently dried in a draft to obtain a substrate having a coating film containing a silicone resin formed on the PET surface.

The results of measuring the icing force of the substrates obtained in Examples 1 to 6 and Comparative Examples 1 to 7 are shown in Table 2.

(Examples 7 to 9, Comparative Example 8)
A substrate-like molded article was obtained in the same manner as in Example 3 except that the amounts of the components A and B were changed to the amounts shown in Table 3, to obtain a substrate-like molded product containing a compound containing a repeating unit represented by Formula (13).

(Comparative example 9)
A substrate-like compact including a compound containing a repeating unit represented by Formula (21) was obtained in the same manner as in Comparative Example 1 except that the preparation amount of the component A was changed to the amount shown in Table 3.

Table 3 shows the results of ice drop measurement of the substrates obtained in Examples 3 and 7 to 9 and Comparative Examples 4 and 8 to the amounts of A component and B component and content of A component in each substrate. It is shown in 3. The relationship between the vinyl methacrylate (A) content and the non-icing recovery rate in the substrates obtained in Examples 3 and 7 to 9 and Comparative Examples 4 and 8 to 9 is shown in FIG.

(Examples 10 to 14, Comparative Example 10)
A substrate-like molded article was obtained in the same manner as in Example 5, except that the amounts of the components A and B were changed to the amounts shown in Table 4, to obtain a substrate-like molded product containing a compound containing a repeating unit represented by Formula (15).

(Comparative example 11)
A substrate-like compact including a compound containing a repeating unit represented by Formula (21) was obtained in the same manner as in Comparative Example 1 except that the preparation amount of the A component was changed to the amount shown in Table 4.

The results of ice drop measurement performed on the substrates obtained in Examples 5, 10 to 14 and Comparative Examples 6 to 10 are shown together with the amounts of A component and B component and content of A component in each substrate. Shown in 4. The relationship between the vinyl methacrylate (A) content and the non-icing recovery rate in the substrates obtained in Examples 5 and 10 to 14 and Comparative Examples 6 and 10 to 11 is shown in FIG.

(Examples 15 to 17 and Comparative Example 13)
A substrate-like molded article was obtained in the same manner as in Example 6, except that the amounts of the components A and B were changed to the amounts shown in Table 5, to obtain a substrate-like molded product containing a compound containing a repeating unit represented by Formula (16).

(Comparative example 12)
A substrate-like compact including a compound containing a repeating unit represented by Formula (26) was obtained in the same manner as in Comparative Example 6 except that the amount of B component was changed to the amount shown in Table 5.

The results of ice drop measurement performed on the substrates obtained in Examples 6, 15 to 17 and Comparative Examples 2 to 12 are shown in the table together with the amounts of A component and B component and content of A component in each substrate. Shown in 5. The relationship between the divinyl adipate (A) content and the non-icing recovery rate in the substrates obtained in Examples 6, 15 to 17 and Comparative Examples 2 and 12 to 13 is shown in FIG.

As is clear from the results shown in Table 2, in the substrate containing the compound obtained by polymerizing the reaction composition of Examples 1 to 6 (the non-icing composition of the present invention), any icing power is used. Below the detection limit (N.D.), it was confirmed that extremely excellent non-icing property was exhibited. Furthermore, as is apparent from the results shown in Tables 2 to 5 and FIGS. 1 to 3, in the substrate, the proportions of the amounts of the crosslinkable monomer (component A) and the radically polymerizable monomer (component B) are specified. It was also confirmed that the non-icing recovery rate is sufficiently high within the above range, and particularly excellent non-icing property is exhibited. For example, in the case of the substrate obtained in Example 7, the contact angle between the substrate surface and the water drop (5 μL of distilled water is dropped on the substrate surface and 25 ° C. using a contact angle meter (manufactured by Kyowa Interface Science) The water repellency is not particularly high at 110 °), but the excellent non-icing property is exhibited as described above, and the non-icing property is not due to the water repellency of the substrate surface, It was also confirmed that the adhesion of ice to the surface is suppressed and exhibited in the interface where the substrate surface and the ice are in contact with each other. In addition, the non-icing recovery rate sometimes decreased due to water droplets adhering to the surface of the substrate, but it was sufficiently recovered by spraying air dried by an air duster or the like on the substrate.
In addition, for example, the substrate obtained in Example 12 has a specific gravity of 1.23 g / cm ³ , and the measurement of the glass transition temperature and the melting point using a thermal analyzer (TG-DTA, manufactured by Mac Science Co., Ltd.) The presence of these was not confirmed, and it was around 120 ° C. that the start of weight loss was confirmed by the same measurement. In addition, no change in appearance or transparency was observed between the substrate and the substrate immediately after production even when it was left at −20 ° C. for 1 month. Furthermore, the thickness of the substrate was 1.8 mm, and the light transmittance was 94% or more when light was incident perpendicularly to the substrate surface.

As described above, according to the present invention, it is possible to provide a non-icing polymer having excellent non-icing properties, and a non-icing composition capable of obtaining the same. . Moreover, since the non-icing polymer of the present invention is also excellent in light transmittance, it can be applied to the surface of various structures where icing is expected, or can be used as a substitute material for the structures.

Claims

The following general formula (1):

[In Formula (1), R 1 represents a hydrogen atom or a methyl group, and R 2 represents a group represented by the following general formula (2):

[In the formula (2), R 3 represents a hydrogen atom or a methyl group. ]
Or a group represented by the following general formula (3):

[In the formula (3), R 4 represents an alkylene group having 1 to 4 carbon atoms, and R 5 represents a hydrogen atom or a methyl group. ]
Represents a group represented by ]
And an ester compound other than the crosslinkable monomer, wherein the crosslinkable monomer is a radically polymerizable monomer having a functional group capable of radically polymerizing with the crosslinkable monomer, and
A ratio of the crosslinkable monomer is 2.5 to 70% by mole based on a total mole of the crosslinkable monomer and the radically polymerizable monomer;
Non-icing composition.
The radical polymerizable monomer is represented by the following general formula (4):

[In the formula (4), R 6 represents an alkyl group having 1 to 8 carbon atoms which may be substituted by a fluorine atom, and R 7 represents a hydrogen atom or a methyl group. ]
The non-icing composition according to claim 1, which is at least one selected from the group consisting of a compound represented by: and diallyl terephthalate.
A non-icing polymer which is a copolymer obtained by polymerizing the crosslinkable monomer and the radical polymerizable monomer in the non-icing composition according to claim 1 or 2.